CN111253610A

CN111253610A - Dynamic polymer foam composite material

Info

Publication number: CN111253610A
Application number: CN202010068682.5A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Tiance Material Technology Co.,Ltd.
Priority date: 2020-01-21
Filing date: 2020-01-21
Publication date: 2020-06-09

Abstract

The invention discloses a dynamic polymer foam composite material, which contains skinned polymer foam particles and a dynamic polymer; wherein, the dynamic polymer contains dynamic covalent bonds and/or supermolecule actions on the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite. The composite material has the characteristics of low density, portability, heat insulation, sound insulation, buffering, shock absorption and dynamic property, and can be widely applied to the manufacture of packaging materials, building materials, shock-resistant protective materials, shock absorption materials, buffering materials, noise reduction materials, heat preservation materials, shape memory materials, electronic and electric appliance materials, medical supplies and the like.

Description

Dynamic polymer foam composite material

Technical Field

The invention relates to the field of intelligent materials, in particular to a dynamic polymer foam composite material.

Background

With the social development, the demand of the consumer market for lightweight, insulating, shock-resistant and sound-damping materials is gradually increasing, and the yield and variety of foam materials are rapidly increasing, making them a very important category of polymer products. Compared with unfoamed materials, the foam material is internally composed of a large number of uniform foam holes with stable size and structure, so that the foam material has the advantages of light weight, heat and sound insulation, high specific strength, buffering and shock absorption, wear resistance and the like, and is widely applied to the fields of packaging industry, agriculture, transportation industry, military industry, aerospace industry, daily necessities and the like.

The traditional foam plastic varieties include thermosetting and thermoplastic foam materials such as polyurethane foam plastic, polystyrene foam plastic, polyethylene foam plastic, polypropylene foam plastic and the like. With the advancement of material science and technology, these traditional thermoset and thermoplastic foam materials have been unable to meet the needs of the rapidly developing high-tech field due to their single structure and properties, and they are also required to be developed toward multi-functionalization and intellectualization.

Disclosure of Invention

The invention is realized by the following technical scheme:

the invention relates to a dynamic polymer foam composite material, which is characterized by comprising skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer comprises at least one dynamic covalent bond in the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

The invention also relates to a dynamic polymer foam composite, characterized in that it comprises skinned polymer foam particles and a dynamic polymer; wherein, the dynamic polymer contains at least one dynamic covalent bond and at least one supramolecular interaction on the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

The invention also relates to a dynamic polymer foam composite, characterized in that it comprises skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains at least two kinds of supramolecules on the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

In the present invention, the dynamic covalent bond includes, but is not limited to, boron-containing dynamic covalent bond, dynamic sulfur bond, dynamic selenium sulfur bond, dynamic selenium nitrogen bond, acetal dynamic covalent bond, dynamic covalent bond based on carbon-nitrogen double bond, dynamic covalent bond based on reversible radical, combinable exchangeable acyl bond, dynamic covalent bond based on induction of steric effect, reversible addition-fragmentation chain transfer dynamic covalent bond, dynamic siloxane bond, dynamic silicon ether bond, exchangeable dynamic covalent bond based on alkyl nitrogen heterocyclic onium, unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction, unsaturated carbon-carbon triple bond capable of alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond, mercapto-Michael addition dynamic covalent bond, An amine alkene-michael addition dynamic covalent bond, a triazolinedione-indole based dynamic covalent bond, a diazacarbene based dynamic covalent bond, a benzoyl based dynamic covalent bond, a hexahydrotriazine based dynamic covalent bond, a dynamic exchangeable trialkylsulfonium bond, a dynamic acid ester bond, a diketene amine dynamic covalent bond.

In the present invention, the supramolecular interactions include, but are not limited to, metal-ligand interactions, hydrogen bonding interactions, halogen bonding interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic interactions (positive and negative ion pairing interactions), ionic clustering interactions, ion-dipole interactions, dipole-dipole interactions, metallophilic interactions, ionic hydrogen bonding interactions, radical cation dimerization, lewis acid-base pairing interactions, host-guest interactions, phase separation, crystallization.

In the present invention, the expandable polymer refers to any suitable polymer which can be prepared into a foam material by a foaming process, and the expandable polymer can have dilatancy or no dilatancy.

In the present invention, the expandable polymer precursor (composition) includes, but is not limited to, a polyol compound, a polyamine compound, a polythiol compound, and an isocyanate compound.

In the present invention, the skinned polymeric foam particles can have high elasticity, plasticity, and dilatancy, including but not limited to, vitrification dilatancy, dynamic dilatancy, entanglement dilatancy, dispersancy dilatancy, and dynamic dilatancy. In the present invention, the dilatancy of the skinned polymeric foam particles can be achieved by using an intrinsic dilatant polymer (i.e., a glassy dilatant polymer, a dynamic dilatant polymer, an entangled dilatant polymer) as the polymer matrix to impart dilatancy to the foam particles, and by blending an intrinsic dilatant polymer component and/or a dispersive dilatant component and/or an aerodynamic dilatant structure in the polymer matrix to impart dilatancy to the foam particles. In the present invention, the composite material may have dilatancy or no dilatancy.

In the present invention, the skinned polymeric foam particles may have dynamic properties achieved by covalently linking dynamic covalent bonds and/or supramolecular interactions, which may include but are not limited to cross-linking, polymerization, branching, in the expandable polymer (composition) or expandable polymer precursor (composition). The foam particles may also have one of ordinary covalent crosslinking, dynamic covalent crosslinking, supramolecular interaction crosslinking, or at least two hybrid crosslinking, preferably supramolecular interaction crosslinking and/or dynamic covalent crosslinking.

In the present invention, the skinned polymer foam particles may have force-responsiveness achieved by covalently attaching force-sensitive groups and/or physically blending force-responsive components in the expandable polymer (composition) or expandable polymer precursor (composition).

In the present invention, the dynamic polymer and its polymer composition with optional components may be foamed or unfoamed.

In a preferred embodiment of the present invention, the expandable polymer used for the preparation of the particles of the skinned polymer foam also contains at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain.

In a preferred embodiment of the invention, the expandable polymer used for the preparation of the particles of the skinned polymer foam also contains at least one force-sensitive group in its polymer chain and/or at least one force-responsive component blended in the polymer; under the action of mechanical force, the force sensitive groups and/or force response components in the foam particles and the expandable polymer are chemically and/or physically changed to realize force response.

The invention also relates to a dynamic polymer foam composite, characterized in that it comprises skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains one of the following supermolecule actions on the polymer chain: metal-ligand interaction, halogen bond interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction (positive and negative ion pair interaction), ion cluster interaction, ion-dipole interaction, dipole-dipole interaction, metallophilic interaction, ionic hydrogen bonding interaction, radical cation dimerization, lewis acid-base pair interaction, host-guest interaction, phase separation, crystallization; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

The invention also relates to a dynamic polymer foam composite, characterized in that it comprises skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains at least one hydrogen bonding group of the following structural components on the polymer chain:

wherein W is selected from oxygen atom and sulfur atom; x is selected from sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from sulfur atoms, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues, preferably from hydrogen atoms; i is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small molecule hydrocarbon group; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small molecule hydrocarbon group;

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, the cyclic group structure can be a micromolecular ring or a macromolecule ring, and the cyclic group structure is preferably a 3-50-membered ring, and more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on each ring-forming atom may or may not be substituted; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite; it has the characteristic of difficult crystallization and is beneficial to forming strong dynamic hydrogen bonds.

In the present invention, the composite material may optionally contain other components such as foam particles, high resilience polymers, plastic polymers, fillers, auxiliaries, etc., in addition to the skinned polymer foam particles and dynamic polymers; the other foam particles may not have a skin structure, and may be prepared by foaming an expandable polymer (composition) or an expandable polymer precursor (composition) to prepare a foamed macro-material, and then cutting, crushing or granulating the foamed macro-material.

The invention also relates to a preparation method of the composite material, which comprises the steps of premixing the skinned polymer foam particles or the polymer particles to be foamed, the dynamic polymer or the raw materials thereof, the optional foaming agent, the optional other auxiliary agents and the optional filling materials, filling the premixed materials into a proper mold, and carrying out hot press molding under certain temperature and pressure conditions to prepare a composite material product; in this process, the matrix (blend) can be selectively foamed depending on the choice of the raw material formulation.

The invention also relates to a preparation method of the composite material, which comprises the steps of premixing the skinned polymer foam particles or the to-be-foamed polymer particles, the dynamic polymer or the raw materials thereof, optional other auxiliary agents and optional fillers, heating and melting by using an extrusion device, mixing a foaming agent before or in the extrusion process, melting and uniformly mixing the foaming agent and the polymer components, extruding the mixture from a machine head through a slit die orifice, and reducing the pressure of a melt flowing through the machine head to form a foaming structure to prepare the composite material product.

The invention also relates to a preparation method of the composite material, which comprises the steps of premixing the belt-skin polymer foam particles or the polymer particles to be foamed, the dynamic polymer or the raw materials thereof, optional other auxiliary agents and optional fillers, then adding the premixed materials into an extruder for melt plasticization, extruding the premixed materials from a head through a slit die orifice, and casting a molten material on a cooled steel material to prepare a composite material product.

The invention also relates to a preparation method of the composite material, which prepares the composite material product by preparing the skinned polymer foam particles or the polymer particles to be foamed, the dynamic polymer or the raw materials thereof, the solvent, the optional foaming agent, the optional other auxiliary agents and the optional fillers into a mixed solution with a certain concentration, then casting the mixed solution on continuously rotating steel at a certain speed, and heating to remove the solvent and solidify the material.

The dynamic polymer foam composite material has the characteristics of low density, light weight, heat insulation, sound insulation, buffering, shock absorption and dynamic property, can be widely applied to the manufacture of packaging materials, building materials, impact-resistant protective materials, shock absorption materials, buffer materials, noise reduction materials, heat preservation materials, shape memory materials, electronic and electrical materials, medical supplies and the like, and is particularly used for manufacturing products with energy absorption and dilatant effects, such as helmet shells, human body protectors, shoe products, sports protection products, military police protection products, automobile buffer parts, automobile interior trim parts, vehicle seats, buffering and shock absorption gaskets, body building equipment protectors, foam parts in ground covering materials and the like.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention provides a dynamic polymer foam composite material containing skin-carrying polymer foam particles and dynamic polymers, wherein the skin-carrying polymer foam particles and the dynamic polymers have characteristics and supplement each other, so that the defects of a single component are overcome, and excellent comprehensive performance is embodied. The foam material prepared by simply utilizing the polymer foam particles for bonding/welding has the advantages that the foam particles are directly exposed under the action of stress, the durability of the foam particles can be influenced after long-term use, the use effect is easily influenced by atrophy and collapse, the performance adjusting means is single, and the density, the elasticity and the shock absorption of the foam material can be adjusted only by the conventional means such as the cell size and the foaming multiplying power; the composite material is filled with dynamic polymers among foam particles, the dynamic polymers among the foam particles not only have the functions of protecting and bonding the foam particles, but also can embody self-repairability, reusability and recyclability by virtue of the dynamic characteristics of the dynamic polymers when the composite material is damaged, and can embody the functional characteristics of shape memory, super toughness and the like in the daily use process, and the dynamic covalent bonds and supermolecule functions contained in the dynamic polymers can be recombined after the composite material is broken, so that the composite material can still keep higher energy absorption effect after being used for multiple times, and the composite material further embodies the functionality compared with the traditional foam material, thereby expanding the application range of the foam material and being put into more frontier and more special fields for use; in addition, the dynamic polymer filled among the foam particles can show different dynamic characteristics and response capabilities under different environmental conditions such as heating, illumination, pH, oxidation reduction and the like, has rich and adjustable self dynamic property, is beneficial to the composite material to absorb energy by utilizing dynamic reversibility, and thus has synergistic buffering and energy absorption effects with the foam particles. Compared with single-component dynamic polymer (foam) materials, the polymer foam particles have the advantages that due to the particularity of the preparation mode, the self foaming ratio is larger, the compressibility is stronger, the weight is lighter, and because the inner foam holes are wrapped by a large amount of air, the foam particles are endowed with more excellent elasticity and high resilience effect, it can generate large compression deformation under the action of external force, can more effectively disperse, absorb and dissipate external impact energy, is more suitable for being used as an energy-absorbing buffer material, is beneficial to improving the defects of single-component dynamic polymer (foam) material in the aspects of weight, rebound resilience, buffering and shock absorption in the practical use, the composite material has dynamic property and high resilience, and the composite material can recover to the original shape as soon as possible after impact or compression, so that the practicability of the material is improved. When the loading of the foam particles reaches above their percolation threshold, the phase formed by the foam particles may serve to support the entire composite and its article; particularly, after the foam particles are bonded/fused, the self-supporting property of the foam particle phase can be reflected; can provide better rebound resilience and structural balance when necessary and reduce the shape memory property in the using process. The composite material can adjust the overall density, dynamic property, flexibility, rebound resilience and buffering and damping performance of the composite material by adjusting the content ratio of the skinned polymer foam particles and the dynamic polymer and the aggregation structure of the skinned polymer foam particles and the dynamic polymer, has higher degree of freedom and preparation simplicity, is favorable for obtaining an intelligent foam product with excellent comprehensive properties such as light weight, high rebound, heat insulation and sound insulation, buffering and damping, self-repairing, recycling and the like by blending and combining the polymer foam particles and the dynamic polymer, and can be widely applied to the manufacture of products such as packaging materials, building materials, impact-resistant protective materials, damping materials, buffering materials, silencing materials, heat-insulating materials, shape memory materials, electronic and electric appliance materials, medical supplies and the like.

(2) The composite material has good designability and controllability. The invention can prepare the composite foam product with different topological structures and appearance characteristics, adjustable performance and wide application by reasonably designing and selecting the polymer types, polymer structures, functional group types and numbers of the expandable polymer and the dynamic polymer which form the skin-carrying polymer foam particles, the cell size and foaming multiplying power of the skin-carrying polymer foam particles in the composite material, the content of the foam particles and the dynamic polymer, the aggregation state structure and other parameters, which is difficult to realize in the existing foam material system. For example, by introducing dynamic covalent bonds and supramolecular effects with different dynamic properties and different strengths into the dynamic polymer, when the dynamic polymer is acted by an external force, the dynamic covalent bonds and supramolecular effects can generate ordered and controllable bond breaking behaviors, so that the dynamic properties of the composite material have orthogonal and/or synergistic effects, the composite material is favorably subjected to controllable self-repairing and dynamic response, and more efficient and abundant dynamic properties and energy absorption capacity are obtained. By introducing force sensitive groups and/or force response components into the polymer foam particles, the foam particle phase and the polymer phase in the composite material can show different force response effects under the action of mechanical force, so that orthogonal and/or synergistic regulation and control on the force response of the composite material are achieved; for another example, dynamic covalent bonds and/or supramolecular effects are introduced into the skin-covered polymer foam particles, so that the foam particle phase in the composite material has dynamic properties, and orthogonal and/or synergistic regulation of the dynamic properties of the composite material can be achieved by respectively regulating and controlling the dynamic properties of the foam particle phase and the polymer phase; for another example, by controlling the aggregation structure of the foam particle phase and the polymer phase and the dilatancy of the two phases, the composite material can be tailored to have different resilience and mechanical strength. The composite material of the present invention exhibits superior and practical functionality compared to conventional foam materials.

(3) In the present invention, the surface structure, particularly the porous structure or the non-porous structure, of the skinned polymer foam particles can be controlled, thereby controlling the amount of the compounded dynamic polymer and other components penetrating into the polymer foam particles, thereby controlling the interfacial force between the foam particles and the dynamic polymer, even the interpenetrating network structure, and thus controlling the properties of the composite material and its products.

(4) The dynamic polymer adopted in the composite material can also show self-repairing property, reusability, recyclability, shape memory, super toughness and the like, so that the composite material prepared by the dynamic polymer has wider application range and longer service life.

Detailed Description

For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or. For example, the expression "realize dilatancy by using strong dynamic supramolecular action and/or strong dynamic property of strong dynamic covalent bond under shearing action" and/or "in the specification means to realize dilatancy by using change of strong dynamic property of strong dynamic supramolecular action under shearing action, or realize dilatancy by using change of strong dynamic property of strong dynamic covalent bond under shearing action, or realize dilatancy by using both strong dynamic supramolecular action and strong dynamic property of strong dynamic covalent bond under shearing action. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.

It should be noted that, in the present invention, the terms "group", "series", "subline", "class", "subclass", "species" used to describe various structures are used to describe groups having a greater scope than the series, a greater scope than the subline, a greater scope than the class, a greater scope than the subclass, and a greater scope than the species, i.e., a group may have a plurality of series, a series may have a plurality of sublines, a subline may have a plurality of classes, a class may have a plurality of subclasses, and a subclass may have a plurality of subclasses. Even if the force-sensitive groups have the same basic structure, differences in properties may occur due to differences in the linking group, substituent, isomer, complex structure, etc. In the present invention, unless otherwise specified, force-sensitive groups having the same basic structure but different structures such as a linker, a substituent, an isomer, and a complex structure are generally regarded as different structures. The invention can reasonably design, select and regulate the force sensitive group according to the requirement to obtain the best performance, which is also the advantage of the invention. In the present invention, when it is desired to use multiple force-sensitive groups, it is preferred to use different types of structures, more preferably different series of structures, for better orthogonality and/or synergistic control.

The term "energy absorption" used in the present invention refers to absorption, dissipation, dispersion, etc. of energy generated by physical impact in the form of impact, vibration, shock, explosion, sound, etc., but does not include absorption of only thermal energy and/or electrical energy, thereby achieving effects such as impact (protection), damping, shock absorption, buffering, sound insulation, noise elimination, etc.

In the present invention, the term "component" includes both chemical/supramolecular chemical structural components and physically mixed components unless otherwise specified. The term "comprising" is intended to mean either a linkage/bond between chemical structures or a physical mixture of specific structures, unless otherwise specified.

In the present invention, the term "common covalent bond" refers to a conventional covalent bond, which is an interaction between atoms through a pair of common electrons, is difficult to break at a common temperature (generally not higher than 100 ℃) and a common time (generally less than 1 day) and has no specific response to mechanical force, and includes, but is not limited to, common carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds, hydrogen-oxygen bonds, nitrogen-nitrogen bonds, etc.

In the present invention, the term "dynamic covalent bond" refers to a type of covalent bond that can be reversibly cleaved and formed under suitable conditions other than the action of mechanical force.

In the present invention, the term "ordinary covalent crosslinking" refers to a crosslinked structure formed only by ordinary covalent bonds. In the present invention, the degree of cross-linking of the common covalent cross-links in the cross-linked network is above its gel point, which means that the cross-linked network is still present when only common covalent bonds (neither dynamic covalent bonds nor supramolecular interactions are present or both are dissociated) are present in the cross-linked network.

In the invention, the "force sensitive group crosslinking" refers to a crosslinking structure formed by the force sensitive group and common covalent bond together, and the crosslinking degree of common covalent crosslinking in a crosslinking network is below the gel point; due to the existence of the force sensitive group, the chemical and/or physical change of the structure can be generated under the action of mechanical force, so that the chemical and/or physical signal change can be directly and/or indirectly generated, new groups/new substances are generated, the specific response to the mechanical force is achieved, and the force response performance/effect is obtained.

In the present invention, the term "dynamic covalent crosslinking" refers to a crosslinked structure formed by dynamic covalent bonds and common covalent bonds, and the crosslinking degree of common covalent crosslinking in the crosslinked network is below the gel point; due to the existence of dynamic covalent bonds, the dissociation-bonding balance of the cross-linked network can be carried out under appropriate conditions, and the dynamic reversibility is realized.

In the present invention, the term "supramolecular interaction crosslinking" refers to a crosslinked structure formed by common participation of supramolecular motifs and common covalent bonds, and the crosslinking degree of common covalent crosslinking in a crosslinked network is below the gel point; due to the existence of the supermolecular unit, the compound can perform cross-linking network dissociation-bonding balance under appropriate conditions and has dynamic reversibility.

In the present invention, the term "hybrid cross-linking" refers to a cross-linked structure formed by at least two of force-sensitive groups, dynamic covalent bonds, supramolecular interactions, and common covalent bonds, wherein the sum of the cross-linking degrees of the cross-linking modes in the cross-linked network is above the gel point. In the embodiment of the present invention, when hybrid crosslinking is present, each crosslinking system may be at least the gel point thereof or less, but the sum of the crosslinking degrees of the crosslinking systems must be at least the gel point of the whole crosslinking system. By combining different dynamic/non-dynamic units in the hybrid cross-linked network, respective advantages can be fully exerted, a synergistic effect can be achieved, and the performance of the material is improved.

In the present invention, the crosslinking degree of the crosslinking (force-sensitive group crosslinking/dynamic covalent crosslinking/supramolecular interaction crosslinking) of a certain component in the crosslinked network is above the gel point, which means that when only ordinary covalent bonds are present in the crosslinked network with this component, the crosslinked network still exists, and when this component is dissociated, the crosslinked network is degraded and can be decomposed into any one or more of the following secondary units: non-crosslinked units such as monomers, polymer chain fragments, polymer clusters, and the like, and even crosslinked polymer fragments, and the like.

The term "polymerization (reaction/action)" used in the present invention refers to a process/action of chain extension, that is, a process of forming a product having a higher molecular weight from a reactant having a lower molecular weight by a reaction form of polycondensation, polyaddition, ring-opening polymerization, etc. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. The product resulting from the polymerization of two or more reactants is referred to as a copolymer. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process of a reactant molecular chain, a branching process of a reactant molecular chain, a ring formation process of a reactant molecular chain, but does not include a crosslinking process of a reactant molecular chain; in embodiments of the invention, "polymerization" encompasses chain growth processes caused by force sensitive groups, dynamic covalent bonds, bonding of common covalent bonds, and supramolecular interactions.

The term "cross-linking (reaction/action)" as used in the present invention refers to the process of generating a three-dimensional infinite network type product by chemical and/or supramolecular chemical linkage between and/or within reactant molecules through the formation of dynamic covalent bonds and/or common covalent bonds and/or supramolecular interactions. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. During the cross-linking of the reactants, the viscosity increases suddenly and gelation begins, the reaction point at which a three-dimensional infinite network is first reached, called the gel point, also called the percolation threshold. A crosslinked reaction product above the gel point (including the gel point, and the degree of crosslinking occurring elsewhere in the present invention includes the gel point in the description above its gel point) having a three-dimensional infinite network structure with the crosslinked network forming a unitary body and spanning the entire polymer structure; the crosslinked reaction products, which are below the gel point, do not form a three-dimensional infinite network structure and do not belong to a crosslinked network that can be integrated across the entire polymer structure. Unless otherwise specified, the term "crosslinked (topological structure) in the present invention includes only a three-dimensional infinite network (structure) having a crosslinking degree of not less than the gel point (including the gel point), and the term" uncrosslinked (structure) refers to a linear, cyclic, branched, etc., and a two-dimensional, three-dimensional cluster, a combination thereof, etc., having a crosslinking degree of not more than the gel point.

In the present invention, the terms used to describe the polymer molecular chain/supramolecular chain topology include, but are not limited to, linear, cyclic, branched, clustered, cross-linked, and combinations thereof.

In the present invention, the "linear" structure refers to a regular or irregular long chain linear shape of a polymer molecular chain, which is generally formed by connecting a plurality of repeating units in a continuous length, and the side groups in the polymer molecular chain generally do not exist as branched chains; for "linear structures," they are generally formed by polymerization of monomers that do not contain long chain pendant groups by polycondensation, polyaddition, ring opening, or the like.

In the present invention, the "cyclic" structure refers to the polymer molecular chain in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple ring, bridge ring, nested ring, grommet, wheel ring, etc.; as the "cyclic structure", it can be formed by intramolecular and/or intermolecular cyclization of a linear or branched polymer, and can also be produced by ring-expanding polymerization or the like.

In the present invention, the "branched" structure refers to a structure containing side chains, branched chains, and branched chains on the polymer molecular chain, including but not limited to star, H, comb, dendritic, hyperbranched, and combinations thereof, and further combinations thereof with linear and cyclic structures, such as linear chain end-linked cyclic structures, cyclic structures combined with comb structures, dendritic chain end-linked cyclic chains, and the like; for "side chain, branched chain and branched chain structures of polymer", it may have a multi-stage structure, for example, one or more stages of branches may be continued on the branches of the polymer molecular chain. As the "branched structure", there are a number of methods for its preparation, which are generally known to those skilled in the art, and which can be formed, for example, by polycondensation of monomers containing long-chain pendant groups, or by chain transfer of radicals during polyaddition, or by radiation and chemical reactions to extend branched structures out of linear molecular chains. The branched structure is further subjected to intramolecular and/or intermolecular reaction (crosslinking) to produce a cluster and a crosslinked structure.

In the present invention, the "cluster" structure refers to a two-dimensional/three-dimensional structure below the gel point generated by intramolecular and/or intermolecular reaction of polymer chains.

In the present invention, the "crosslinked" structure refers to a three-dimensional infinite network structure of a polymer.

In the present invention, the topology may also include a combination of the above topologies. The "combination type" structure refers to a polymer structure containing two or more of the above topological structures, for example, a ring-shaped chain is used as a side chain of a comb-shaped chain, the ring-shaped chain has side chains to form a ring-shaped comb-shaped chain, the ring-shaped chain and a straight chain form a tadpole-shaped chain and a dumbbell-shaped chain, and the combination structure also includes different rings, different branches, different clusters and combination structures of other topological structures.

In the present invention, the "backbone" refers to the chain length direction of the polymer chain. The "crosslinked network chain skeleton" refers to any chain segment constituting the crosslinked network skeleton. The term "main chain" as used herein, unless otherwise specified, refers to the chain having the highest number of links in the polymer structure. The side chain refers to a chain structure which is connected with a polymer main chain skeleton or a crosslinking network chain skeleton in a polymer structure and is distributed beside the chain skeleton, and the molecular weight of the chain structure is more than 1000 Da; wherein the branched or branched chain refers to a chain structure with a molecular weight of more than 1000Da branched from a polymer main chain skeleton or a cross-linked network chain skeleton or any other chain; in the present invention, for the sake of simplicity, the side chain, the branched chain, and the branched chain are collectively referred to as a side chain unless otherwise specified. Wherein, the side group refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with the polymer chain skeleton and distributed beside the chain skeleton in the polymer structure. For the side chain and the side group, the side chain and the side group can have a multi-stage structure, that is, the side chain can be continuously provided with the side group and the side chain, the side chain of the side chain can be continuously provided with the side group and the side chain, and the side chain also comprises chain structures such as branched chain and branched chain. The "terminal group" refers to a chemical group which is linked to the polymer chain skeleton in the polymer structure and is located at the end of the chain skeleton; in the present invention, the side groups may have terminal groups in specific cases. For hyperbranched and dendritic chains and their related chain structures, the polymer chains therein can be regarded as main chains, but in the present invention, the outermost chains are regarded as side chains and the remaining chains as main chains, unless otherwise specified. In the present invention, the "side chain", "side group" and "end group" also apply to small molecular monomers and large molecular monomers that undergo supramolecular polymerization by supramolecular action. For non-crosslinked structures, the polymer chain skeleton comprises a polymer main chain skeleton and chain skeletons such as polymer side chains, branched chains and the like; for the crosslinked structure, the polymer chain skeleton includes a skeleton of an arbitrary segment present in the crosslinked network (i.e., crosslinked network chain skeleton) and chain skeletons thereof such as side chains, branched chains, and branched chains.

In the invention, the boron-containing dynamic covalent bond contains boron atoms in the dynamic structure composition, and includes but is not limited to fifteen types of bonds, i.e. organic boron anhydride bond, inorganic boron anhydride bond, organic-inorganic boron anhydride bond, saturated five-membered ring organic borate bond, unsaturated five-membered ring organic borate bond, saturated six-membered ring organic borate bond, unsaturated six-membered ring organic borate bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, organic borate monoester bond, inorganic borate monoester bond, organic borate silicone bond and inorganic borate silicone bond; wherein, each boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. When two or more boron-containing dynamic covalent bonds are selected, the boron-containing dynamic covalent bonds can be selected from different structures in the same type of boron-containing dynamic covalent bonds, and also can be selected from different structures in different types of boron-containing dynamic covalent bonds, wherein, in order to achieve orthogonal and/or synergistic dynamic performance, the boron-containing dynamic covalent bonds are preferably selected from different structures in different types of boron-containing dynamic covalent bonds.

In the present invention, the organoboron anhydride linkages are selected from, but not limited to, at least one of the following structures:

wherein each boron atom in the organoboron anhydride linkage is connected to at least one carbon atom by a boron-carbon bond, and at least one organic group is connected to the boron atom by said boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom

Can be linked to form a ring, on different boron atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organoboronic anhydride bond structures may be exemplified by:

in the embodiment of the present invention, the organoboron anhydride linkages, which may be formed by reacting organoboronic acid moieties contained in the compound starting materials with organoboronic acid moieties, may be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups contained in the compound starting materials containing organoboron anhydride linkages.

In the present invention, the inorganic boron anhydride linkage is selected from, but not limited to, the following structures:

wherein, Y₁、Y₂、Y₃、Y₄Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,Oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, preferably from oxygen atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y₃、Y₄At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c, d denote each independently of Y₁、Y₂、Y₃、Y₄The number of connected connections; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from silicon atoms, a, b, c and d are 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic boron anhydride bond structures are exemplified by:

in the embodiment of the present invention, the inorganic boron anhydride bond may be formed by the reaction of an inorganic boric acid moiety contained in the compound raw material with an inorganic boric acid moiety, or may be introduced into the polymer by the polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic boron anhydride bond.

In the present invention, the organic-inorganic boron anhydride linkage is selected from, but not limited to, the following structures:

wherein, Y₁、Y₂Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1, Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b denote independently from Y₁、Y₂The number of connected connections; when Y is₁、Y₂When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is₁、Y₂When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is₁、Y₂When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is₁、Y₂When each is independently selected from silicon atoms, a, b is 3; difference on the same atom

Can be linked to form a ring, on different atoms

The ring may be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organic-inorganic boron anhydride bond structures may be exemplified by:

in embodiments of the present invention, the organic-inorganic boron anhydride linkages, which may be formed by reaction of organic boronic acid moieties contained in the compound starting materials with inorganic boronic acid moieties, may also be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups contained therein using compound starting materials containing organic-inorganic boron anhydride linkages.

In the invention, the saturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:

wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the saturated five-membered ring organic boronic acid ester bond can be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an organic boronic acid moiety, or a polymer can be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring organic boronic acid ester bond.

In the invention, the unsaturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated five-membered ring organic borate bond may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an organic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring organic borate bond.

In the present invention, the saturated six-membered ring organic borate bond is selected from, but not limited to, the following structures:

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronate bond structures may be exemplified by:

in the embodiment of the present invention, the saturated six-membered ring organoboronate bond may be formed by reacting a 1, 3-diol moiety contained in a compound raw material with an organoboronate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a saturated six-membered ring organoboronate bond.

In the present invention, the unsaturated six-membered ring organic borate bond is selected from, but not limited to, the following structures:

wherein the boron atom is bonded to a carbon atom via a boron-carbon bond and has at least one organic groupThe group is connected to the boron atom through the boron-carbon bond;

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

The electricity may be connected in a ring. Typical unsaturated six-membered ring organoboronate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated six-membered ring organoboronate bond may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an organoboronate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring organoboronate bond.

In the invention, the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably selected from boron atoms and aminomethyl benzene groups in the structure (B)

Denotes the position bonded to the boron atom) Connecting; the organic boric acid units for forming the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably aminomethyl phenylboronic acid (ester) units.

As the aminomethyl phenylboronic acid (ester) element has higher reaction activity when reacting with the 1, 2-diol element and/or the catechol element and/or the 1, 3-diol element and/or the 2-hydroxymethylphenol element, the formed boron-containing dynamic covalent bond has stronger dynamic reversibility, can perform dynamic reversible reaction under milder neutral conditions, can show sensitive dynamic characteristics and obvious energy absorption effect, and can embody greater advantages when being used as an energy absorption material.

Typical structures of such boron-containing dynamic covalent bonds with aminomethyl benzene groups are exemplified by:

in the invention, the saturated five-membered ring inorganic borate ester bond is selected from but not limited to at least one of the following structures:

wherein, Y₁Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a is 3; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring inorganic borate bond structures are exemplified by:

in the embodiment of the present invention, the saturated five-membered ring inorganic borate bond may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring inorganic borate bond.

In the present invention, the unsaturated five-membered ring inorganic borate ester bond is selected from, but not limited to, at least one of the following structures:

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a is 3;

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be replaced byAny substituent may be substituted or unsubstituted. Typical unsaturated five-membered ring inorganic borate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated five-membered ring inorganic borate bond may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an inorganic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring inorganic borate bond.

In the present invention, the saturated six-membered ring inorganic borate bond is selected from, but not limited to, at least one of the following structures:

wherein, Y₁Selected from oxygen atoms, sulphur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably oxygen atoms;

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring inorganic borate bond structures may be exemplified by:

in the embodiment of the present invention, the saturated six-membered ring inorganic borate bond may be formed by reacting a 1, 3-diol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated six-membered ring inorganic borate bond.

In the present invention, the unsaturated six-membered ring inorganic borate bond is selected from, but not limited to, at least one of the following structures:

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or can be connected into a ring. Typical unsaturated six-membered ring inorganic borate bond structures are exemplified by:

in the embodiment of the present invention, the unsaturated six-membered ring inorganic borate bond may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an inorganic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring inorganic borate bond.

In the invention, the organoboronic acid monoester bond is selected from but not limited to at least one of the following structures:

wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms

A divalent non-carbon atom, a linking group containing at least two backbone atoms;

an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom(ii) a Different in the same carbon atom, boron atom

Can be connected into a ring, on different carbon atoms and boron atoms

Can also be connected into a ring or can be connected with I₁、I₂The substituent atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to an aliphatic ring, an ether ring, a condensation ring and a combination thereof, wherein the organic boric acid single ester bond formed after the 6 and 7 structures form the ring is not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond which are described in the previous description. Typical organic boronic acid monoester bond structures are exemplified by:

in the embodiment of the present invention, the organoboronate monoester bond may be formed by reacting a monol moiety contained in a compound raw material with an organoboronic acid moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing an organoboronate monoester bond.

In the present invention, the inorganic boronic acid monoester bond is selected from, but not limited to, at least one of the following structures:

wherein, Y₁～Y₁₃Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂；Y₃、Y4；Y₅、Y₆、Y₇、Y₈；Y₉、Y₁₀、Y₁₁、Y₁₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is₁₄Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a to n each represent a linkage to Y₁～Y₁₄The number of connected connections; when Y is₁～Y₁₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is₁～Y₁₄When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is₁～Y₁₄When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is₁～Y₁₄Each independently selected from silicon atoms, a to n is 3;

an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Can also be connected into a ring or can be connected with I₁、I₂Wherein the substituents (substituents) form a ring, said ring including but not limited to aliphatic ring, ether ring, condensed ring and combinations thereof, wherein 5, 6, 7,The inorganic boric acid monoester bond formed after the 8-structure ring formation is not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond. Typical inorganic boronic acid monoester bond structures are exemplified by:

in the embodiment of the present invention, the inorganic boronic acid monoester bond can be formed by reacting a monol moiety contained in a compound raw material with an inorganic boronic acid moiety, and a polymer can also be introduced by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the inorganic boronic acid monoester bond.

In the invention, the organic boric acid silicon ester bond is selected from but not limited to at least one of the following structures:

wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereofAnd (6) mixing. Typical silicon organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the organoboronate silicone bond may be formed by reacting a silanol moiety contained in the compound raw material with an organoboronic acid moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an organoboronate silicone bond.

In the present invention, the inorganic borate silicone bond is selected from, but not limited to, at least one of the following structures:

wherein, Y1, Y₂Y3 are each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c denote each independently of Y₁、Y₂、Y₃The number of connected connections; when Y is₁、Y₂、Y₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is₁、Y₂、Y₃When each is independently selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is₁、Y₂、Y₃When each is independently selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is₁、Y₂、Y₃When each is independently selected from silicon atoms, a, b and c are 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic silicon borate ester bond structures include, for example:

in the embodiment of the present invention, the inorganic borate silicone bond may be formed by reacting a silanol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic borate silicone bond.

The organic boronic acid moiety in the embodiments of the present invention is selected from, but not limited to, any of the following structures:

wherein, K₁、K₂、K₃Is a monovalent organic group or a monovalent organosilicon group directly bonded to an oxygen atom through a carbon atom or a silicon atom, selected from any of the following structures: small molecule hydrocarbyl, small molecule silyl, polymer chain residues; k₄Is a divalent organic or divalent organosilicon group directly attached to two oxygen atoms, directly attached to the oxygen atoms through a carbon or silicon atom, selected from any of the following structures: a divalent small molecule hydrocarbon group, a divalent small molecule silane group, a divalent polymer chain residue; m₁ ⁺、M₂ ⁺、M₃ ⁺Is a monovalent cation, preferably Na⁺、K⁺、NH₄ ⁺；M₄ ²⁺Is divalentCations, preferably from Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺；X₁、X₂、X₃Is a halogen atom, preferably selected from chlorine and bromine atoms; d₁、D₂Is a group bound to a boron atom, D₁、D₂Are different and are each independently selected from hydroxyl (-OH), ester (-OK)₁) Salt group (-O)^-M₁ ^*) Halogen atom (-X)₁) Wherein, K is₁、M₁ ⁺、X₁The definitions of (A) and (B) are consistent with those described above, and are not described herein again; wherein, the boron atom in the structure is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

The inorganic boronic acid moiety described in the embodiments of the present invention is selected from, but not limited to, the following structures:

wherein, W₁、W₂、W₃Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and W₁、W₂、W₃At least one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;

denotes crosslinking with polymer chainsA network chain or any other suitable group/atom linkage, wherein x, y, z each independently represent a linkage to W₁、W₂、W₃The number of connected connections; when W is₁、W₂、W₃X, y, z is 0 when each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; when W is₁、W₂、W₃When each is independently selected from oxygen atom and sulfur atom, x, y and z are 1; when W is₁、W₂、W₃When each is independently selected from nitrogen atom and boron atom, x, y and z are 2; when W is₁、W₂、W₃Each independently selected from the group consisting of silicon atom, x, y, z ═ 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

The inorganic boric acid moiety described in the embodiment of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate ester, inorganic boron halide as a raw material.

The 1, 2-diol moiety described in the embodiments of the present invention is ethylene glycol

And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;

the 1, 3-diol moiety described in the embodiments of the present invention is 1, 3-propanediol

for the 1, 2-diol moiety and the 1, 3-diol moiety, they may be linear structures or cyclic group structures.

For linear 1, 2-diol motif structures, it may be selected from any one or several of the B-like structures and isomeric forms thereof:

class B:

for linear 1, 3-diol motif structures, it may be selected from any one or several of the C-like structures and isomeric forms thereof:

class C:

wherein R is₁～R₃Is a monovalent group attached to the 1, 2-diol moiety; r₄～R₈Is a monovalent group attached to the 1, 3-diol moiety;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein R is₁～R₈Each independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group and polymer chain residue.

Wherein, the isomeric forms of B1-B4 and C1-C6 are respectively and independently selected from any one of position isomerism, conformational isomerism and chiral isomerism.

For a cyclic 1, 2-diol elementary structure, two carbon atoms in an ethylene glycol molecule are connected through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1, 2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:

for cyclic 1, 3-diol motif structures, it can be formed by linking two carbon atoms in the 1, 3-propanediol molecule through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1, 2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:

the catechol moiety in the present invention is a catechol

And substituted forms thereof, hybridized forms thereof, and combinations thereof, having lost at least one non-hydroxyl hydrogen atom, suitable catechol motif structures being exemplified by:

the 2-hydroxymethylphenol moiety described in the present invention is a 2-hydroxymethylphenol

And substituted forms thereof and hybridized forms thereof and combinations thereof, with suitable 2-hydroxymethylphenol motifs such as:

the monool moiety in the embodiment of the present invention refers to a structural moiety consisting of a hydroxyl group and a carbon atom directly bonded to the hydroxyl group (

Wherein, the carbon atom can be a non-aromatic carbon atom, and can also be an aromatic carbon atom), and in the case that the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit form an unsaturated/saturated five-membered ring organic borate bond, an unsaturated/saturated six-membered ring organic borate bond, an unsaturated/saturated five-membered ring inorganic borate bond and an unsaturated/saturated six-membered ring inorganic borate bond, the monoalcohol unit is not the hydroxyl group in the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit, and besides this, the monoalcohol unit can also be selected from any suitable dihydric (polybasic) alcohol compound and/or any hydroxyl group in the group. Suitable structures containing monoalcohol moieties may be mentioned, for example:

the silanol moiety in the embodiment of the present invention refers to a structural moiety consisting of a silicon atom and a hydroxyl group or a group hydrolyzable to the silicon atom to obtain a hydroxyl group (

Wherein Z can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate group, borate group, acyl, acyloxy, acylamino, ketoxime group, alkoxide group and the like, and preferably halogen and alkoxy).

The boron-containing dynamic covalent bond selected by the invention has strong dynamic property and mild dynamic reaction condition, can realize the synthesis and dynamic reversible effect of the polymer under the conditions of no need of a catalyst, no need of high temperature, illumination or specific pH, can further improve the preparation efficiency, reduce the limitation of the use environment and expand the application range of the polymer.

In the present invention, the boron-free dynamic covalent bond does not contain boron atom in its dynamic structure composition, and includes, but is not limited to, dynamic sulfur linkage, dynamic selenium sulfur linkage, dynamic selenium nitrogen linkage, acetal dynamic covalent linkage, dynamic covalent linkage based on carbon-nitrogen double bond, dynamic covalent linkage based on reversible free radical, exchangeable acyl linkage, dynamic covalent linkage based on steric effect induction, reversible addition-fragmentation chain transfer dynamic covalent linkage, dynamic siloxane linkage, dynamic silicon-ether linkage, exchangeable dynamic covalent linkage based on alkyl nitrogen heterocyclic onium, unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction, unsaturated carbon-carbon triple bond capable of alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, boron atom-free dynamic covalent linkage, and reversible free radical-based on reversible free radical, and exchangeable acyl linkage, Twenty-seven groups of bonds including a mercapto-Michael addition dynamic covalent bond, an amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a benzoyl-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, a dynamically exchangeable trialkylsulfonium bond, a dynamic acid ester bond and a diketoenamine dynamic covalent bond; wherein, each group of boron-free dynamic covalent bonds can contain a plurality of types of boron-free dynamic covalent bond structures. When two or more than two boron-free dynamic covalent bonds are selected, the boron-free dynamic covalent bonds can be selected from different structures in the same type of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, different structures in different types of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, and different structures in different groups of boron-free dynamic covalent bonds, wherein in order to achieve orthogonal and/or synergistic dynamic performance, the boron-free dynamic covalent bonds are preferably selected from different structures in different groups of boron-free dynamic covalent bonds.

In the invention, the dynamic sulfur-connecting bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, which can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic sulfur linkage described in the present invention is selected from the following structures:

wherein x is the number of S atoms, x is more than or equal to 2,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic sulfur linkage structures may be exemplified by:

in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating dynamic sulfur-connecting bond includes, but is not limited to, temperature adjustment, addition of oxidation-reduction agent, addition of catalyst, addition of initiator, light irradiation, radiation, microwave, plasma action, pH adjustment and the like, for example, the dynamic sulfur-connecting bond can be broken to form sulfur radical by heating, so that the dynamic sulfur-connecting bond is dissociated and exchanged, the dynamic sulfur-connecting bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability, light irradiation can also lead the dynamic sulfur-connecting bond to be broken to form sulfur radical, so that the dissociation and exchange reaction of disulfide bond can be carried out, the dynamic sulfur-connecting bond is reformed after removing the light irradiation, so that the polymer can obtain self-repairability and reworkability, radiation, microwave and plasma can generate radical in the system to act with the dynamic sulfur-connecting bond, so that the self-repairability and reworkability can be obtained, so that the dynamic sulfur-connecting bond can be formed and exchanged, so that the process is accelerated and the self-repairability can be obtained, wherein the dynamic reversible catalyst includes, the dynamic hydrogen peroxide-oxidizing agent can be obtained by adding the hydrogen peroxide-oxidizing agent, the hydrogen peroxide-oxidizing agent can also include, the hydrogen peroxide-oxidizing agent can be obtained by heating, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-bis-2-bis-phenyl-bis-phenyl-2-bis-phenyl-thiobenzone-2-bis (2-ethyl-bis (2-phenyl-bis-phenyl-ethyl-phenyl-ethyl-ketone-ethyl-2-bis (2-phenyl-bis-phenyl-bis (2-phenyl-bis (2-phenyl-ethyl-phenyl-ethyl-ketone), the hydrogen peroxide-ketone-bis (2-phenyl-ethyl-phenyl-2-phenyl-ketone), the hydrogen peroxide-bis (2-ethyl-phenyl-bis (2) initiator, 2-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-phenyl-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-bis (4) initiator, 2-bis (2) initiator, 2-bis (2.

In the embodiment of the present invention, the dynamic sulfur linkage may be formed by a bonding reaction of a sulfur radical through an oxidative coupling reaction of a mercapto group contained in a compound raw material, or may be introduced into a polymer through a polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a disulfide linkage. Among these, the compound raw material containing a disulfide bond is not particularly limited, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide, sulfur, and mercapto compound containing a disulfide bond are preferable, and a polyol, isocyanate, epoxy compound, alkene, and alkyne containing a disulfide bond are more preferable.

In the invention, the dynamic selenium-connecting bond comprises a dynamic double selenium bond and a dynamic multiple selenium bond, which can be activated under certain conditions and generate bond dissociation, bonding and exchange reaction to embody dynamic reversible characteristics; the dynamic selenium linkage bond in the invention is selected from the following structures:

wherein x is the number of S atoms, x is more than or equal to 2,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.

Typical dynamic selenium linkage structures may be mentioned, for example:

in the embodiment of the invention, the dynamic reversible conditions for activating the dynamic selenium bond include, but are not limited to, temperature adjustment, addition of redox initiator, addition of catalyst, addition of initiator, irradiation, radiation, microwave, plasma action and the like, so that the polymer shows good self-repairability, recycling recoverability, stimulation responsiveness and the like, for example, heating can lead the dynamic selenium bond to be broken to form selenium free radicals, so that dissociation and exchange reaction of the dynamic bond can be generated, the dynamic selenium bond is reformed and stabilized after cooling, self-repairability and reprocessing can be shown, the polymer containing the dynamic bond can obtain good self-repairing performance through laser irradiation, the free radicals can be generated in the system to react with the dynamic selenium bond through irradiation, microwave and plasma, so that self-repairability and reprocessing can be obtained, the dynamic polymer can also be recycled through adding the redox agent in the system, wherein the reductive agent can promote the dynamic selenium bond to be dissociated to be selenol, so that the dynamic polymer is dissociated, the oxidative agent can form the dynamic selenium bond, so that the dynamic bond can be obtained, so that the dynamic polymer can be dissociated to form the dynamic selenol, so that the dynamic selenol can obtain the dynamic reversible initiator, the dynamic selenol, the initiator can be converted into the dynamic peroxybenzoxy bond, the dynamic peroxybenzoxy-benzoxy-2-bis- (tert-2-propyl-2- (tert-butyl-propyl-benzoyl benzoxy-2-benzoyl-benzoxy-2-propyl-2-dimethyl-propyl-2-dimethyl-2-dimethyl-propyl-2-propyl-benzoxy-dimethyl-2-dimethyl-propyl-2-propyl-2-dimethyl-propyl-2-dimethyl-propyl-benzoxy-2-dimethyl-2-propyl-benzoxy-propyl-2-propyl-2-dimethyl-propyl-2-dimethyl-propyl-dimethyl-2-dimethyl-propyl.

In the embodiment of the present invention, the dynamic selenium linkage may be formed by an oxidative coupling reaction of selenol contained in the compound raw material or a bonding reaction of a selenium radical, or may be introduced into the polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic selenium linkage. Among these, the raw material of the compound having a kinetic selenium linkage is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, and a diselenide having a kinetic selenium linkage (e.g., sodium diselenide and dichlorodiselenide) are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a kinetic selenium linkage are more preferable.

In the invention, the dynamic selenium-sulfur bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing the dynamic reversible characteristic; the dynamic selenium-sulfur bond in the invention is selected from at least one of the following structures:

wherein the content of the first and second substances,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium-sulfur bond structures may be exemplified by:

in the present embodiment, the "conditions" for activating dynamic reversibility of dynamic selenothio bond includes, but is not limited to, temperature adjustment, addition of redox agent, addition of catalyst, addition of initiator, irradiation, microwave, plasma action, etc., such that the polymer exhibits good self-repairability, recycling recoverability, stimulus responsiveness, etc., for example, heating may cause the dynamic selenothio bond to be broken to form a sulfur radical and a selenium radical, thereby causing dissociation and exchange reaction of the dynamic bond, and cooling may cause the dynamic selenothio bond to be reformed and stabilized, thereby exhibiting self-repairability and reprocessing, such that the polymer containing the selenothio bond may obtain good self-repairing performance by laser irradiation, such that radicals may be generated in the system by irradiation, microwave and plasma to interact with the dynamic selenothio bond to obtain self-repairability and reprocessing, such that the dynamic polymer may also obtain recycling recoverability by adding redox agent in the system, wherein the species of the reducing agent include, but not limited to, sodium hyposulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, tris (2-oxoethyl-2-oxoethyl) phosphine, tris (2-oxopropyl-bis (2-benzoylphosphine) peroxide, bis (2-benzoyl-2-bis (2-oxopropyl-oxoketone) peroxide, bis (2-oxopropyl-oxoketone, bis (2-oxoketone) peroxide, 2-oxoketone, 2-oxopropyl-oxoketone, 2-oxoketone, 2-oxoketone-oxoether, 2-oxoketone.

In the embodiment of the present invention, the dynamic selenothio bond may be formed by a bond formation reaction of a sulfur radical and a selenium radical through an oxidative coupling reaction of thiol and selenol contained in the compound raw materials, or may be introduced into the polymer through a polymerization/crosslinking reaction between reactive groups contained in the compound raw materials containing a selenothio bond. Among these, the raw material of the compound having a sulfur-selenium bond is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a sulfur-selenium bond are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a sulfur-selenium bond are more preferable.

In the invention, the dynamic selenium-nitrogen bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic selenium nitrogen bond described in the present invention is selected from the following structures:

wherein X is selected from halogen ions, preferably chloride ions and bromide ions,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium nitrogen bond structures can be exemplified by:

in the embodiments of the present inventionThe "certain condition" for activating the dynamic reversibility of the dynamic selenium nitrogen bond includes, but is not limited to, temperature regulation, addition of an acid-base catalyst, and the like, so that the polymer exhibits good self-repairability, recycling property, stimulus responsiveness, and the like. Wherein, the acid-base catalyst can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.

In an embodiment of the present invention, the dynamic selenazonitrogen bond can be formed by reacting a selenium halide contained in a compound raw material with a pyridine derivative.

In the invention, the acetal dynamic covalent bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioketal bond, can be activated under certain conditions, and generates bond dissociation, ketal reaction and exchange reaction, thus showing dynamic reversible characteristics; the "certain conditions" for activating the dynamic reversibility of acetal dynamic covalent bond means heating, appropriate acidic aqueous conditions, and the like. The acetal-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein, X₁、X₂、X₃、X₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom, preferably from oxygen atom, sulfur atom; r₁、R₂Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r₃、R₄Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical acetal-based dynamic covalent bond structures include, for example:

in the embodiment of the present invention, the acetal dynamic covalent bond can be dissociated in an acidic aqueous solution and formed under anhydrous acidic conditions, and has good pH stimulus responsiveness, so that dynamic reversibility can be obtained by adjusting an acidic environment.

In embodiments of the present invention, acids that may be used in the dynamic ketal reaction include, but are not limited to, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, oxalic acid, carbonic acid, propionic acid, nonanoic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzenesulfinic acid, p-methoxybenzoic acid, 1, 4-phthalic acid, 4, 5-difluoro-2-nitrophenylacetic acid, 2-bromo-5-fluorophenylpropionic acid, bromoacetic acid, chloroacetic acid, phenylacetic acid, adipic acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation. The invention can also use different states of the acid in a combined mode, such as promoting the formation of dynamic covalent bonds by using an organic solution of p-toluenesulfonic acid, and dissociating the dynamic covalent bonds by using an aqueous solution of hydrochloric acid to obtain recycling property and the like.

In the embodiment of the present invention, the acetal dynamic covalent bond may be formed by condensation reaction of a ketone group, an aldehyde group, a hydroxyl group, and a thiol group contained in a compound raw material, may be formed by exchange reaction of an acetal dynamic covalent bond with an alcohol, a thiol, an aldehyde, and a ketone, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing an acetal dynamic covalent bond. Among these, the raw material of the compound having the acetal dynamic covalent bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the acetal dynamic covalent bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the acetal dynamic covalent bond are more preferable.

According to the invention, the dynamic covalent bond based on the carbon-nitrogen double bond comprises a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond and a dynamic acylhydrazone bond, and can be activated under certain conditions, and dissociation, condensation and exchange reactions of the dynamic covalent bond are carried out, so that the dynamic reversible characteristic is embodied; herein, the "certain condition" for activating the dynamic covalent bond dynamic reversibility based on a carbon-nitrogen double bond refers to an appropriate pH aqueous condition, an appropriate catalyst presence condition, a heating condition, a pressurizing condition, and the like. The dynamic covalent bond based on carbon-nitrogen double bond in the invention is selected from at least one of the following structures:

wherein R is₁Is a divalent or polyvalent small molecule hydrocarbon group;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic covalent bond structures based on carbon-nitrogen double bonds may be mentioned, for example:

in the embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic covalent bond based on carbon-nitrogen double bond refers to that the dynamic polymer is swelled in an aqueous solution with a certain pH value or the surface thereof is wetted with an aqueous solution with a certain pH value, so that the dynamic covalent bond based on carbon-nitrogen double bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution selected varies depending on the type of the selected dynamic covalent bond based on carbon-nitrogen double bond, for example, for the dynamic phenylimide bond, an acidic solution having a pH of 6.5 or less may be selected for hydrolysis, and for the dynamic acylhydrazone bond, an acidic solution having a pH of 4 or less may be selected for hydrolysis.

Wherein, the acid-base catalyst for the dissociation, condensation and exchange reaction of the dynamic covalent bond based on carbon-nitrogen double bond can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Group IA alkali metals and compounds thereof, for example, lithium oxide, acetylLithium acetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, brilliant carbonate and the like. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.

In the embodiment of the present invention, the dynamic covalent bond based on carbon-nitrogen double bond may be formed by condensation reaction of ketone group, aldehyde group, acyl group and amino group, hydrazine group, hydrazide group contained in the compound raw material, or may be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic covalent bond based on carbon-nitrogen double bond. Among these, the raw material of the compound having a dynamic covalent bond based on a carbon-nitrogen double bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a carbon-nitrogen double bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a carbon-nitrogen double bond are more preferable.

In the invention, the dynamic covalent bond based on the reversible free radical can be activated under certain conditions to generate free radicals and generate bonding or exchange reaction of the bond, thus showing dynamic reversible characteristics; the "exchange reaction of dynamic covalent bonds based on reversible free radicals" means that intermediate state free radicals formed after the dissociation of old dynamic covalent bonds in the polymer form new dynamic covalent bonds elsewhere, thereby generating exchange of chains and change of polymer topology. The reversible radical-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein each W is independently selected from an oxygen atom, a sulfur atom;

wherein, W₁Each independently selected from single bonds, ether groups, thioether groups, secondary amine groups and substituents thereof, divalent methyl groups and substituents thereof, preferably from direct bonds, ether groups, thioether groups; w at different positions₁Are the same or different;

wherein, W₂Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, divalent methyl groups and substituents thereof, preferably from thioether groups, secondary amine groups; w at different positions₂Are the same or different;

wherein, W₃Each independently selected from ether groups, thioether groups, preferably ether groups; w at different positions₃Are the same or different;

wherein, W₄Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, preferably from ether groups; w at different positions₄Are the same or different;

wherein V, V ' are independently selected from carbon atom and nitrogen atom, different positions have the same or different structure of V, V ', when V, V ' is selected from nitrogen atom, the compound is connected with V, V

Is absent;

wherein Z is selected from selenium atom, tellurium atom, antimony atom and bismuth atom; wherein k is linked to Z

The number of (2); when in useWhen Z is a selenium atom or a tellurium atom, k is 1, and represents only one

Is connected with Z; when Z is an antimony atom or a bismuth atom, k is 2, which means that there are two

To Z are two

Are the same or different in structure;

wherein R is₁Each independently selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; r₁Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene_1-20Hydrocarbyl/heterohydrocarbyl; r₁Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;

wherein R is₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; each R is₂Are the same or different; when R is₂When selected from substituents, it is selected from, but not limited to: hydroxy, phenyl, phenoxy, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group;

wherein R is₃Each independently selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10Alkylaminoacyl, phenyl, substituted phenyl, arylalkyl, substituted arylalkyl; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group;

wherein R is¹、R²、R³、R⁴Each independently selected from hydrogen atom, halogen atom, heteroatom group, substituent; r¹、R²、R³、R⁴Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl and combinations of two or more of the foregoing; more preferably from hydrogen atom, hydroxy group, cyano group, carboxy group, C_1-20Alkyl radical, C_1-20Heteroalkyl, cyclic structure C_1-20Alkyl, C of cyclic structure_1-20Heteroalkyl group, C_1-20Aryl radical, C_1-20A heteroaryl group;

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is⁵、R⁶、R⁷、R⁸When each is independently selected from the group consisting of a substituent, the substituent is preferably a substituent having a steric hindrance effect; the substituents with steric hindrance are selected from, but not limited to: cyano radicals, C_1-20Alkyl radical, C_1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; by way of example, typical sterically hindered substituents include, but are not limited to: cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexylAlkyl, adamantyl, phenyl, pyridyl, C_1-5Alkyl-substituted phenyl, C_1-5Alkoxy-substituted phenyl, C_1-5Alkylthio-substituted phenyl, C_1-5Alkylamino substituted phenyl, cyano substituted phenyl;

wherein each L is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; l is each independently preferably selected from the group consisting of acyl, acyloxy, acylthio, acylamino, oxyacyl, thioacyl, phenylene, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C_1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C_1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group₁To the carbon atom(s) of (a);

wherein the content of the first and second substances,

represents that the ring has a conjugated structure; wherein the content of the first and second substances,

is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,

the two five-membered nitrogen heterocycles form a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond between the two ring-forming atoms; according to different connection modes, the connection modes are different,

including but not limited to one or more of the following isomers:

it should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs described above are regarded as the same structural motif in the present invention;

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one ring-forming atom in the ring-forming atoms of the aliphatic heterocyclic ring is a nitrogen atom, the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms and silicon atoms, and hydrogen atoms connected to the ring-forming atoms are substituted or not substituted by any suitable substituent atoms, substituents; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; said

Preferably at least one of the following structures, but the invention is not limited thereto:

said

More preferably at least one of the following structures, but the present invention is not limited thereto:

wherein the content of the first and second substances,

is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are optionally substituted by any suitable substituent atom, substituent group or not; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Of an aromatic ring of (a) in different positions

Are the same or different; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each one ofAn

The structures are the same or different; is different

Typical dynamic covalent bond structures based on reversible free radicals may be mentioned, for example:

wherein, W, W₁、W₂、W₃、W₄、

The definition, selection range and preferable range of (2) are as described above.

In an embodiment of the present invention, the "certain conditions" for activating dynamic reversibility of dynamic covalent bond based on reversible free radical include, but are not limited to, temperature adjustment, addition of initiator, light irradiation, radiation, microwave, plasma action, etc., for example, the dynamic covalent bond may be cleaved to form a free radical by heating, thereby causing dissociation and exchange reaction of the dynamic covalent bond, and the dynamic covalent bond may be reformed and stabilized after cooling, thereby allowing self-repairing and re-processing of the polymer, the light irradiation, microwave and plasma may also cause cleavage of the dynamic covalent bond to form a free radical, thereby causing dissociation and exchange reaction of the dynamic covalent bond, and the dynamic covalent bond may be reformed after removing the light irradiation, thereby causing self-repairing and re-processing, wherein the initiator is capable of generating a free radical in the system, thereby facilitating dissociation or exchange of the dynamic covalent bond, thereby obtaining self-repairing or re-processing, and recycling, wherein the initiator includes, but is not limited to, any one or several of photo-initiator, such as 2, 2-dimethoxy-2-benzoyl peroxide (2-benzoylbenzophenone), bis (2-bis (4-butyl-2-benzoyl) -2-bis (4-butyl-benzoylbenzophenone) peroxybenzophenone, 2-bis (4-butyl-phenyl) peroxybenzophenone), bis (4-oxopropyl-2-propyl-2-bis (tert-butyl-2-oxopropyl-2-butyl-2-oxopropyl-2-oxopropyl-4-2-oxopropyl-2-4-2-4-oxopropyl-2-bis (preferably, preferably-bis (4-2-.

In an embodiment of the present invention, the reversible radical-based dynamic covalent bond contained in the polymer may be formed by a bonding reaction or other suitable coupling reaction of radicals contained in the compound raw materials; it can be generated in situ in the polymer or can be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups it contains using a compound starting material containing a dynamic covalent bond based on a reversible free radical. Among these, the raw material of the compound having a dynamic covalent bond based on a reversible radical is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a reversible radical are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a reversible radical are more preferable.

In the present invention, the binding exchangeable acyl bond can be activated under certain conditions and undergoes a binding acyl exchange reaction (e.g., a binding transesterification reaction, a binding amide exchange reaction, a binding carbamate exchange reaction, a binding vinylogous amide or vinylogous carbamate exchange reaction, etc.) with a nucleophilic group, thereby exhibiting a dynamic reversible property; wherein, the 'associative acyl exchange reaction' means that the associative exchangeable acyl bonds are firstly combined with nucleophilic groups to form an intermediate structure, and then the acyl exchange reaction is carried out to form a new dynamic covalent bond, thereby generating exchange of chains and change of a topological structure of the polymer, wherein the crosslinking degree of the polymer can be kept unchanged; wherein the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond means suitable catalyst existence conditions, heating conditions, pressurizing conditions, etc.; the "nucleophilic group" refers to a reactive group such as hydroxyl, sulfhydryl and amino group, which is present in a polymer system for a binding acyl exchange reaction, and the nucleophilic group may be on the same polymer network/chain as the binding exchangeable acyl bond, may be on a different polymer network/chain, or may be introduced through a small molecule or a polymer containing the nucleophilic group. The binding exchangeable acyl bond as described in the present invention is selected from at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z₁、Z₂Selected from oxygen atom, sulfur atom; r₅Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X₁、X₂When it is an oxygen atom or a sulfur atom, R₁、R₂、R₃、R₄Is absent; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Wherein the binding exchangeable acyl bond is preferably selected from the group consisting of a binding exchangeable ester bond, a binding exchangeable thioester bond, a binding exchangeable amide bond, a binding exchangeable urethane bond, a binding exchangeable thiocarbamate bond, a binding exchangeable urea bond, a binding exchangeable vinyl amide bond, and a binding exchangeable vinyl carbamate bond. Typical binding exchangeable acyl bond structures may be exemplified by:

among them, the acyl bond having an exchangeable binding property to a nucleophilic group is more preferable, and typical structures thereof are, for example:

in the present invention, some of the bonded acyl exchange reactions need to be carried out under catalytic conditions, and the catalysts include catalysts for transesterification (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange (including amides, carbamates, thiocarbamates, ureas, vinylogous amides, vinylogous carbamates, etc.). By adding the catalyst, the occurrence of the combined acyl exchange reaction can be promoted, so that the dynamic polymer shows good dynamic characteristics.

Wherein the catalyst for the transesterification reaction may be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate, and cobalt carbonate. (3) The alkali metal of group IIA and its compounds are exemplified by calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, and magnesium ethoxide. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, and an aluminum alkoxide-based compound can be cited. (5) Tin compounds include inorganic tin compounds and organic tin compounds. Examples of the inorganic tin include tin oxide, tin sulfate, stannous oxide, and stannous chloride. Examples of the organotin include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tin tributylacetate, tributyltin chloride and trimethyltin chloride. (6) Examples of the group IVB element compound include titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium oxide, zirconium sulfate, zirconium tungstate, and tetramethyl zirconate. (7) Anionic layered column compounds, the main component of which is generally composed of hydroxides of two metals, called double metal hydroxides LDH, and the calcined product of which is LDO, such as hydrotalcite { Mg }₆(CO₃)[Al(OH)₆]₂(OH)₄·4H₂O }. (8) Supported solid catalysts, which may be mentioned by way of example KF/CaO, K₂CO₃/CaO、KF/γ-Al₂O₃、K₂CO₃/γ-Al₂O₃、KF/Mg-La、K₂O/activated carbon, K₂CO₃Coal ash powder, KOH/NaX, KF/MMT (montmorillonite) and other compounds. (9) Examples of the organozinc compound include zinc acetate and zinc acetylacetonate. (10) Examples of the organic compound include 1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, and the like. Among them, preferred are organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, 2-MI; more preferably, TBD and zinc acetate are mixed and used for concerted catalysis, and 2-MI and zinc acetylacetonate are mixed and used for concerted catalysis.

Among them, the catalyst for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) Montmorillonite KSF, hafnium tetrachloride (HfCl)₄)、Hf₄Cl_sO₂₄H₂₄、HfCl₄KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as copper acetate; examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, copper acetate is preferable; sc (OTf)₃And HfCl₄Mixing and sharing synergistic catalysis; HfCl₄KSF-polyDMAP; the glycerol, the boric acid and the ferric nitrate hydrate are mixed to share the synergistic catalysis.

In the present embodiment, some of the coupling acyl exchange reactions may be performed by microwave irradiation or heating. For example, common urethane bonds, thiourethane bonds and urea bonds can be heated to 160-180 ℃ under the pressure of 4MPa to perform acyl exchange reaction; the vinylogous amide bond and the vinylogous carbamate bond can generate acyl exchange reaction through Michael addition when being heated to more than 100 ℃;

the urethane bond of the structure can be heated to more than 90 ℃ to carry out acyl exchange reaction with the molecular chain containing the phenolic hydroxyl or the benzyl hydroxyl structure. The present invention preferably performs the reversible reaction under normal temperature and normal pressure conditions by adding a catalyst that can be used for the binding acyl exchange reaction.

In the embodiment of the present invention, the binding exchangeable acyl bond may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acid halide, an acid anhydride, an active ester, an isocyanate group, a hydroxyl group, an amino group, and a thiol group contained in the compound raw material, or may be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the binding exchangeable acyl bond. Among these, the starting material of the compound having the exchangeable acyl bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the exchangeable acyl bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the exchangeable acyl bond are more preferable.

In the invention, the dynamic covalent bond based on steric effect induction contains a large group with steric effect, can be activated at room temperature or under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic. The steric effect induced dynamic covalent bond as described in the present invention is selected from at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, silicon atoms and nitrogen atoms, preferably carbon atoms, nitrogen atoms; z₁、Z₂Selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R is_bIs a bulky group with steric hindrance directly bonded to the nitrogen atom, and is selected from C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl, most preferably selected from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl;

nitrogen-containing rings having an arbitrary number of atoms, which may be aliphatic rings or aromatic rings, which may be aliphatic rings, aromatic rings, ether rings, condensed rings, or combinations thereof, wherein the ring-forming atoms are each independently selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or another hetero atom, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not, and the resulting rings are preferably pyrrole rings, imidazole rings, pyrazole rings, piperidine rings, pyridine rings, pyridazine rings, pyrimidine rings, or pyrazine rings; n represents the number of linkages to the ring-forming atoms of the cyclic group structure. Typical steric effect-based induced dynamic covalent bond structures may be exemplified by:

the "bulky group having steric hindrance" as referred to in the present invention is directly bonded to a nitrogen atom or forms a cyclic structure with a nitrogen atomThe method can weaken the chemical bond strength between carbon atoms and adjacent nitrogen atoms in carbonyl and thiocarbonyl, so that the carbon-nitrogen bond shows the property of a dynamic covalent bond, and the dynamic reversible reaction can be carried out at room temperature or under certain conditions. It is to be noted that the larger the steric effect in the "bulky group having steric effect" is, the better, the moderate size is, and the appropriate dynamic reversibility of the carbon-nitrogen bond is provided. The 'certain condition' for activating dynamic covalent bond dynamic reversibility induced by steric effect comprises but is not limited to action modes of heating, pressurizing, lighting, radiation, microwave, plasma action and the like, so that the polymer has good self-repairing property, recycling property, stimulus responsiveness and the like. For example,

the dynamic covalent bond of the structure can carry out dynamic exchange reaction at 60 ℃, and shows dynamic characteristics.

In the present invention, the steric effect induced dynamic covalent bond is preferably selected from steric effect induced amide bond, steric effect induced urethane bond, steric effect induced thiourethane bond, and steric effect induced urea bond.

In the embodiment of the present invention, the steric effect induced dynamic covalent bond may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acyl halide, an acid anhydride, an active ester, an isocyanate group contained in a compound raw material and an amino group to which a bulky group having steric effect is attached, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the steric effect induced dynamic covalent bond. Among these, the raw material of the compound having a dynamic covalent bond induced by steric hindrance is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, or a carboxylic acid having a dynamic covalent bond induced by steric hindrance is preferably contained, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, or an alkyne having a dynamic covalent bond induced by steric hindrance is more preferably contained.

In the invention, the reversible addition fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator, and a reversible addition fragmentation chain transfer reaction is carried out, so that the dynamic reversible characteristic is embodied. The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein R is₁～R₁₀Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x₁、X₂、X₃Each independently selected from single bond, divalent or polyvalent small molecule hydrocarbon group, preferably from divalent C_1-20Alkyl groups and substituted forms thereof, hybridized forms thereof, and combinations thereof, more preferably selected from the group consisting of divalent isopropyl groups, divalent cumyl groups, divalent isopropyl ester groups, divalent isopropylcarboxyl groups, divalent isopropyl nitrile groups, divalent nitrile cumyl groups, divalent acrylic acid group n-mers, divalent acrylic ester group n-mers, divalent styrene group n-mers and substituted forms thereof, hybridized forms thereof, and combinations thereof, wherein n is greater than or equal to 2; z₁、Z₂、Z₃Each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbyl group, preferably from a heteroatom linking group having or associated with a group having an electro-absorption effect, a divalent or polyvalent small molecule hydrocarbyl group having or associated with a group having an electro-absorption effect; wherein as Z₂、Z₃Preferably, it can be selected from the group consisting of ether group, sulfide group, selenium group, divalent silicon group, divalent amine group, divalent phosphoric acid group, divalent phenyl group, methylene group, ethylene group, divalent styrene group, divalent isopropyl group, divalent cumyl group, divalent isopropyl ester group, divalent isopropylcarboxyl group, divalent isopropylnitrile group, divalent nitrile cumyl group; wherein, the group with the electric absorption effect includes but is not limited to carbonyl, aldehyde group, nitro, ester group, sulfonic group, amido, sulfone group, trifluoromethyl, aryl, cyano, halogen atomAlkenes, alkynes, and combinations thereof;

The reversible addition fragmentation chain transfer dynamic covalent bonds described herein are preferably polyacrylic and ester groups, polymethacrylic and ester groups, polystyrene, polymethylstyrene, allyl sulfide groups, dithioester groups, diseleno groups, trithiocarbonate groups, triselenocarbonate groups, diseleno thiocarbonate groups, dithioselenocarbonate groups, bisthioester groups, bisseleno groups, bistrothiocarbonate groups, bistriselenocarbonate groups, dithiocarbamato groups, diseleno carbamate groups, dithiocarbonate groups, diseleno carbonate groups, and derivatives thereof.

Typical reversible addition fragmentation chain transfer dynamic covalent bond structures may be exemplified by:

wherein n is the number of the repeating units, can be a fixed value or an average value, and n is more than or equal to 1.

The "reversible addition fragmentation chain transfer reaction" described in the present invention means that when a reactive radical reacts with the reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention to form an intermediate, the intermediate can be fragmented to form a new reactive radical and a new reversible addition fragmentation chain transfer dynamic covalent bond, and this process is a reversible process. This process is similar to, but not exactly identical to, the reversible addition fragmentation chain transfer process in reversible addition fragmentation chain transfer polymerization. Firstly, reversible addition fragmentation chain transfer polymerization is a solution polymerization process, and the reversible addition fragmentation chain transfer reaction can be carried out in solution or solid; in addition, in the reversible addition fragmentation chain transfer reaction, a proper amount of a substance capable of generating an active free radical can be added to generate the active free radical under a certain condition, so that the reversible addition fragmentation chain transfer dynamic covalent bond has good dynamic reversibility, and the progress of the reversible addition fragmentation chain transfer reaction is promoted.

Wherein, the initiator optionally used in the reversible addition-fragmentation chain transfer exchange reaction includes, but is not limited to, any one or any of photoinitiators such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and α -ketoglutaric acid, organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylperoxypivalate, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides such as dimethoxyacetophenone, potassium peroxydisulfate, etc., preferably, 2-dimethoxybenzoyl peroxybenzoate, ammonium persulfate, and azobenzoperoxydisulfonitrile.

In embodiments of the present invention, the reversible addition fragmentation chain transfer dynamic covalent bond may be introduced into the polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using a compound starting material containing the reversible addition fragmentation chain transfer dynamic covalent bond.

In the invention, the dynamic siloxane bond can be activated under the condition of catalyst or heating, and siloxane exchange reaction is carried out, so that the dynamic reversible property is embodied; the term "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere with concomitant dissociation of old siloxane bonds, resulting in exchange of chains and a change in polymer topology. A dynamic siloxane linkage as described in the present invention, selected from the following structures:

wherein the content of the first and second substances,

may be looped or not looped.

In the present invention, the siloxane reaction is carried out in the presence of a catalyst or under heating, wherein the dynamic siloxane bond is preferably subjected to a siloxane bond exchange reaction in the presence of a catalyst. The catalyst can promote the siloxane equilibrium reaction, so that the dynamic polymer has good dynamic characteristics. Among them, the catalyst for the siloxane equilibrium reaction can be selected from: (1) examples of the alkali metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, and calcium hydroxide. (2) Examples of the alkali metal alkoxide and the alkali metal polyalcohol salt include potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutoxide, sodium t-butoxide, potassium t-butoxide, lithium pentoxide, potassium ethylene glycol, sodium glycerol, potassium 1, 4-butanediol, sodium 1, 3-propanediol, lithium pentaerythritol, and sodium cyclohexanolate. (3) Examples of the silicon alkoxide include potassium triphenylsilanolate, sodium dimethylphenylsilicolate, lithium tri-tert-butoxysilicolate, potassium trimethylsilolate, sodium triethylsilanolate, lithium (4-methoxyphenyl) dimethylsilolate, tri-tert-pentoxysilicolate, potassium diphenylsilanediol, and potassium benzyltrimethylammonium bis (catechol) phenylsilicolate. (4) Examples of the quaternary ammonium base include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylbenzylammonium hydroxide, tetrabutylammonium hydroxide, (1-hexadecyl) trimethylammonium hydroxide, methyltriethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetra-N-hexylammonium hydroxide, tetrapropylammonium hydroxide, tetraoctylammonium hydroxide, triethylbenzylammonium hydroxide, choline, [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, phenyltriethylammonium hydroxide, N, N, N-trimethyl-3- (trifluoromethyl) aniline hydroxide, N-ethyl-N, N-dimethyl-ethylammonium hydroxide, tetradecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, N-trimethyl-1-adamantylammonium hydroxide, N-ethylbutylammonium hydroxide, N-dodecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, N-trimethyl-1-adamantylammonium hydroxide, and mixtures thereof, Forty-eight alkyl ammonium hydroxide, N-dimethyl-N- [3- (sulfo-oxo) propyl ] -1-nonane ammonium hydroxide inner salt, (methoxycarbonyl sulfamoyl) triethyl ammonium hydroxide, 3-sulfopropyl dodecyl dimethyl betaine, 3- (N, N-dimethyl palmityl amino) propane sulfonate, methacryloyl ethyl sulfobetaine, N-dimethyl-N- (3-sulfopropyl) -1-octadecane ammonium inner salt, tributyl methyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, tetradecyl sulfobetaine, etc. In the present invention, the catalyst used for the siloxane equilibrium reaction is preferably a catalyst of quaternary ammonium base, silanol type, or alkali metal hydroxide type, and more preferably a catalyst of lithium hydroxide, potassium trimethylsilanolate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), or the like.

In the embodiment of the present invention, the dynamic siloxane bond may be formed by a condensation reaction between a silicon hydroxyl group and a silicon hydroxyl group precursor contained in the compound raw material, or may be introduced into the polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic siloxane bond. Among these, the raw material of the compound having a dynamic siloxane bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosiloxane compound, an epoxy compound, an alkene, and an alkyne having a dynamic siloxane bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosiloxane compound, and an alkene having a dynamic siloxane bond are more preferable. Wherein the silicon hydroxyl precursorThe term "body" means a structural element consisting of a silicon atom and, attached to the silicon atom, a group which can be hydrolyzed to give a hydroxyl group (Si-X)₁) Wherein X is₁Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃，Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂，Si-ONa。

In the invention, the dynamic silicon ether bond can be activated under heating condition, and silicon ether bond exchange reaction is carried out, thus showing dynamic reversible characteristic; the "exchange reaction of the silyl ether bond" refers to the formation of a new silyl ether bond elsewhere with concomitant dissociation of the old silyl ether bond, resulting in exchange of the chains and a change in the topology of the polymer. A dynamic silicon ether linkage as described in the present invention selected from the following structures:

wherein the content of the first and second substances,

may be looped or not looped. Among them, the dynamic silicon ether bond is more preferably selected from the following structures:

in one embodiment of the present invention, the dynamic silicon ether bond is a silicon ether bondThe polymer can be formed by condensation reaction of silicon hydroxyl group and silicon hydroxyl group precursor contained in the compound raw material and hydroxyl group in the system, or can be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing dynamic silicon ether bond. Among these, the raw material of the compound having a dynamic silicon ether bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosilation compound, an epoxy compound, an alkene, and an alkyne having a dynamic silicon ether bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosilation compound, and an alkene having a dynamic silicon ether bond are more preferable. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom₁) Wherein X is₁Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃，Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂，Si-ONa。

In the invention, the exchangeable dynamic covalent bond based on the alkyl azacyclo-onium can be activated under certain conditions and has dynamic exchange reaction with halogenated alkyl, thus showing dynamic reversible characteristics. The exchangeable dynamic covalent bond based on azacyclium in the present invention is selected from at least one of the following structures:

wherein, X is negative ion selected from bromide ion and iodide ion, preferably bromide ion;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical alkylazacyclonium-based exchangeable dynamic covalent bond structures are exemplified by:

in the embodiment of the present invention, the haloalkyl group, which may be an aliphatic haloalkyl group or an aromatic haloalkyl group, may be present in any suitable terminal group, side group and/or side chain in the dynamic polymer, or may be present in any suitable form in other components such as small molecules, oligomers, etc., and may be on the same polymer network/chain with exchangeable dynamic covalent bonds based on alkyl nitrogen azides, or on different polymer networks/chains, or may be introduced through small molecules or polymers containing haloalkyl groups.

In the present embodiment, the "certain conditions" for activating the dynamic reversibility of the exchangeable dynamic covalent bond based on the alkylazacyclonium means in the presence of the halogenated alkyl group and the solvent and under suitable conditions of temperature, humidity, pressure, etc.

In the embodiment of the present invention, the alkyl nitrogen heterocyclic onium-based exchangeable dynamic covalent bond can be formed by the action of triazolyl/pyridyl compound and halogenated hydrocarbon, and can also be introduced into polymer by the polymerization/crosslinking reaction between the reactive groups contained in the raw material of the compound containing alkyl nitrogen heterocyclic onium-based exchangeable dynamic covalent bond, wherein the triazolyl compound can be formed by the reaction of azide group contained in the raw material of the compound and alkyne, wherein the halogenated hydrocarbon includes, but is not limited to, saturated halogenated hydrocarbon (for example, methyl chloride, bromocyclohexane, 1, 2-dibromoethane, triiodomethane, etc.), unsaturated halogenated hydrocarbon (for example, vinyl bromide, 3-chlorocyclohexene, 4-bromo-1-butene-3-alkyne, 1-bromo-2-iodocyclobutene, etc.), halogenated aromatic hydrocarbon (for example, chlorobenzene, β -bromonaphthalene, benzyl chloride, o-dichlorobenzene, etc.), etc., wherein the raw material of the compound containing alkyl nitrogen heterocyclic onium-based dynamic covalent bond is not particularly limited, and preferably, the raw material of the compound containing alkyl nitrogen heterocyclic onium-based exchangeable dynamic covalent bond, polyvalent alcohol, epoxy-containing epoxy-vinyl chloride, isocyanate, epoxy-based compound, epoxy-vinyl chloride, isocyanate, etc.

In the invention, the unsaturated carbon-carbon double bond capable of generating olefin cross metathesis double decomposition reaction can be activated in the presence of a catalyst and generates olefin cross metathesis double decomposition reaction, thus showing dynamic reversible characteristic; wherein, the olefin cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by metal catalyst; wherein, the rearrangement reaction refers to the generation of new carbon-carbon double bonds at other places and the dissociation of old carbon-carbon double bonds, thereby generating the exchange of chains and the change of polymer topological structure. The structure of the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction in the present invention is not particularly limited, and is preferably selected from the following structures having low steric hindrance and high reactivity:

in embodiments of the present invention, the catalyst for catalyzing olefin cross metathesis reaction includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, etc.; among them, the catalyst is preferably a catalyst based on ruthenium, molybdenum, tungsten, more preferably a ruthenium catalyst having higher catalytic efficiency and being insensitive to air and water, particularly a catalyst which has been commercialized such as Grubbs 'first generation, second generation, third generation catalysts, Hoveyda-Grubbs' first generation, second generation catalysts, etc. Among these, examples of catalysts useful in the present invention for catalyzing olefin cross metathesis reactions include, but are not limited to, the following:

wherein Py is₃Is composed of

Mes is

Ph is phenyl, Et is ethyl, i-Pr is isopropyl, t-Bu is tert-butyl, and PEG is polyethylene glycol.

In the invention, the unsaturated carbon-carbon triple bond capable of generating alkyne cross metathesis reaction can be activated in the presence of a catalyst and generate alkyne cross metathesis reaction, thus showing dynamic reversible characteristic; wherein, the alkyne cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; the rearrangement reaction refers to the formation of new triple bonds between carbon and the dissociation of old triple bonds between carbon and carbon, resulting in exchange of chains and change of polymer topology. The structure of the unsaturated carbon-carbon triple bond in which the alkyne cross metathesis reaction can occur in the present invention is not particularly limited, and is preferably selected from the structures shown below which are small in steric hindrance and high in reactivity:

in embodiments of the present invention, the catalyst for catalyzing alkyne cross-metathesis reaction includes, but is not limited to, metal catalysts based on molybdenum, tungsten, and the like; among them, the catalyst is preferably a catalyst having compatibility with the functional group, such as catalysts 15 to 20 in the exemplified structure, etc.; the catalyst is also preferably a catalyst having higher catalytic efficiency and being insensitive to air, such as catalysts 1, 18-20, etc. in the exemplified structure; the catalyst is also preferably a catalyst which can function catalytically at ambient temperature or in the ambient temperature range, such as catalyst 11 in the illustrated construction. Examples of catalysts useful in the present invention for catalyzing alkyne cross metathesis reactions include, but are not limited to, the following:

wherein Py is₃Is composed of

Ph is phenyl and t-Bu is tert-butyl.

In the embodiment of the present invention, the unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction and the unsaturated carbon-carbon triple bond capable of alkyne cross metathesis reaction may be derived from a selected polymer precursor containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or may be generated or introduced on the basis of a polymer precursor containing no unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond. However, since the reaction conditions for forming the carbon-carbon double bond/carbon-carbon triple bond are generally harsh, it is preferable to use a polymer precursor having carbon-carbon double bond/carbon-carbon triple bond to carry out the reaction, thereby achieving the purpose of introducing carbon-carbon double bond/carbon-carbon triple bond.

Among them, polymer precursors which already contain unsaturated carbon-carbon double bonds/unsaturated carbon-carbon triple bonds include, by way of example and not limitation, butadiene rubber, 1, 2-butadiene rubber, isoprene rubber, polynorbornene, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polychloroprene, brominated polybutadiene, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), unsaturated polyester, unsaturated polyether and its copolymer, 1, 4-butylene glycol, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, unsaturated carbon-carbon triple bonds, Glyceryl monoricinoleate, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloromaleic acid, 2-methylenesuccinic acid (itaconic acid), 4' -diphenylenedicarboxylic acid, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, fumaroyl chloride, 1, 4-phenylenediacryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, dimethyl citraconate, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene, etc., and oligomers having a carbon-carbon double bond/carbon-carbon triple bond in the terminal-functionalized chain skeleton may also be used.

In the invention, the [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein, the [2+2] cycloaddition reaction refers to a reaction that one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively provide 2 pi electrons to react and add with each other to form a quaternary ring structure. The [2+2] cycloaddition dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein D is₁～D₆Each independently selected from carbon atom, oxygen atom, sulfur atom, selenium atom, nitrogen atom, silicon atom, preferably from carbon atom, D₁、D₂At least one of them is selected from carbon atom or oxygen atom or nitrogen atom or silicon atom; a is₁～a₆Respectively represent with D₁～D₆The number of connected connections; when D is present₁～D₆Each independently selected from oxygen atom, sulfur atom, selenium atom₁～a₆0; when D is present₁～D₆Each independently selected from nitrogen atoms, a₁～a₆1 is ═ 1; when D is present₁～D₆Each independently selected from carbon atom and silicon atom, a₁～a₆＝2；Q₁～Q₆Each independently selected from carbon atoms, oxygen atoms; b₁～b₆Respectively represent and Q1-Q₆The number of connected connections; when Q is₁～Q₆Each independently selected from oxygen atoms, b₁～b₆0; when Q is₁～Q₆Each of which isIndependently from carbon atoms, b₁～b₆＝2；

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typically [2+2]]Examples of cycloaddition dynamic covalent bond structures are:

in an embodiment of the present invention, the unsaturated double bond for performing the [2+2] cycloaddition reaction may be selected from a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-sulfur double bond, a carbon-nitrogen double bond, a nitrogen-nitrogen double bond; unsaturated triple bonds, which may be selected from carbon-carbon triple bonds, for forming said [2+2] cycloaddition dynamic covalent bond; wherein, the unsaturated double bond and the unsaturated triple bond are preferably directly connected with an electroabsorption effect group or an electrosupply effect group, and the electroabsorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro, ester group, sulfonic group, acylamino, sulfonyl, trifluoromethyl, aryl, cyano, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.

In the embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond can be formed by [2+2] cycloaddition reaction between unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, cumulative diene groups, and ketene groups contained in compound raw materials, or between the unsaturated carbon-carbon triple bonds and the compound raw materials, or can be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw materials containing the [2+2] cycloaddition dynamic covalent bond, wherein the compound raw materials containing the unsaturated carbon-carbon double bonds are preferably ethylene, propylene, acrolein, acrylonitrile, acrylic ester, methacrylic ester, butenedicarboxylic acid, cinnamyl alcohol, cinnamyl aldehyde, cinnamic acid, cinnamyl amide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compounds, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene, and derivatives of the above compounds, and the like, and the raw materials containing the [2+2] cycloaddition dynamic covalent bond are not particularly limited, and preferably contain a compound containing a compound of [2+2] cycloaddition, a polyvalent alcohol, a thiol group, a compound containing an alkyne, a thiol group, a compound containing a thiol group, a compound.

In the invention, the [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group and 2 pi electrons are provided by a dienophile group to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein, K₁、K₂、K₅～K₁₀Each independently selected from carbon atom, oxygen atom, sulfur atom, and nitrogen atomSilicon atom, selenium atom, and at K₁、K₂Or K₅、K₆Or K₇、K₈Or K₉、K₁₀At least one atom selected from carbon atom, nitrogen atom or silicon atom; c. C₁～c₁₀Respectively represent and K₁～K₁₀The number of connected connections; when K is₁、K₂、K₅～K₁₀Each independently selected from oxygen atom, sulfur atom, selenium atom, c₁、c₂、c₅～c₁₀0; when K is₁、K₂、K₅～K₁₀Each independently selected from nitrogen atoms, c₁、c₂、c₅～c₁₀1 is ═ 1; when K is₁、K₂、K₅～K₁₀Each independently selected from carbon atom and silicon atom, c₁、c₂、c₅～c₁₀＝2；K₃、K₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C₃、c₄Respectively represent and K₃、K₄The number of connected connections; when K is₃、K₄Each independently selected from an oxygen atom and a sulfur atom, c₃、c₄0; when K is₃、K₄Each independently selected from nitrogen atoms, c₃、c₄＝1；I₁、I₂Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, an amide group, an ester group, a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, a 1, 1' -vinyl group, substituted forms of a secondary amine group, an amide group, an ester group;

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein when the ring-forming atoms are selected from nitrogen atomsThe nitrogen atom may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical [4+2]]Examples of cycloaddition dynamic covalent bond structures are:

wherein, the [4+2] cycloaddition dynamic covalent bond can be connected with the light-control locking element to form the light-control DA structure. The light-operated locking element can react with the dynamic covalent bond and/or the light-operated locking element under a specific illumination condition to change the structure of the dynamic covalent bond, thereby achieving the purpose of locking/unlocking DA reaction; wherein, when the dynamic covalent bond is locked, it is unable or more difficult to perform DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it is able to perform DA equilibrium reaction, realizing dynamic characteristics.

In the invention, the light control locking element comprises the following structural units:

wherein the content of the first and second substances,

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;

a photo-controlled [4+2] cycloaddition dynamic covalent bond attached to a photo-control locking motif, preferably selected from at least one of the following general structures:

wherein, K₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₃、K₄Or K₅、K₆At least one of them is selected from carbon atoms; a is₁、a₂、a₃、a₄、a₅、a₆Respectively represent and K₁、K₂、K₃、K₄、K₅、K₆The number of connected connections; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from an oxygen atom and a sulfur atom₁、a₂、a₃、a₄、a₅、a₆0; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from nitrogen atoms, a₁、a₂、a₃、a₄、a₅、a₆1 is ═ 1; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atoms, a₁、a₂、a₃、a₄、a₅、a₆＝2；I₁、I₂、I₃Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1, 1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1, 1' -vinyl group and substituted forms thereof; when I is₁、I₂、I₃Each independently absent, b ═ 2; when I is₁、I₂、I₃Each independently selected from the group consisting of an oxygen atom, a 1, 1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1, 1' -vinyl group and substituted forms thereof, and b is 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (

n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c₁、C₂、C₃、C₄、C₅、C₆Represent carbon atoms in different positions; difference on the same atom

Can be linked to form a ring, on different atoms

Can also be linked to form a ring, where K is preferred₁And K₂K to₃And K₄K to₅And K₆C to₁And C₂C to₃And C₄C to₅And C₆Forming a ring; the resulting ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, each of which has ring atomsThe hydrogen atoms on the ring-forming atoms can be substituted by any substituent or not; wherein, K₁And K₂K to₃And K₄K to₅And K₆The ring formed between preferably has the following structure:

C₁and C₂C to₃And C₄The ring formed between preferably has the following structure:

C₅and C₆The ring formed between preferably has the following structure:

in the embodiment of the present invention, the diene group used for the [4+2] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and its derivatives, etc.; dienophile groups for forming the [4+2] cycloaddition dynamic covalent bonds containing any suitable unsaturated double or triple bonds, such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-sulfur double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, and the like; wherein, the diene group, unsaturated double bond or unsaturated triple bond in the dienophile group are preferably directly connected with the electric absorption effect group or the electric supply effect group, and the electric absorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro group, ester group, sulfonic group, acylamino group, sulfonyl group, trifluoromethyl, aryl, cyano group, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.

In the embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond can be formed by [4+2] cycloaddition reaction between a compound raw material containing a diene group and a compound raw material containing a dienophile group, or a polymer can be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a [4+2] cycloaddition dynamic covalent bond, wherein the compound raw material containing a diene group can be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives of the above compounds, and wherein the compound raw material containing a dienophile group can be selected from ethylene, propylene, acrolein, acrylonitrile, acrylic ester, methacrylic ester, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, dithioether, maleimide, and derivatives of the above compounds containing a [4+2] cycloaddition, and more preferably a compound containing a cycloaddition of a [4+2] cycloaddition, a fullerene, a compound containing a fullerene group, a thiol group, and a compound containing no more preferably a cycloaddition of a compound containing a cycloaddition of a polyvalent alkene, a thiol group, a compound containing a thiol group, and a compound containing a thiol group, and a.

In the invention, the [4+4] cycloaddition dynamic covalent bond is formed based on the [4+4] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing dynamic reversible characteristics; wherein the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 pi electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond described in the present invention is selected from the following structures:

wherein the content of the first and second substances,

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring, aza benzene, aza naphthalene, aza anthracene and substituted forms of the above groups; i is₆～I₁₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;

Can be linked to form a ring, on different atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typically [4+4]]Examples of cycloaddition dynamic covalent bond structures are:

in an embodiment of the present invention, the conjugated diene group used for the [4+4] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as benzene, anthracene, naphthalene, furan, cyclopentadiene, cyclohexadiene, pyrone, pyridone and its derivatives, and the like.

In the embodiment of the present invention, the [4+4] cycloaddition dynamic covalent bond may be formed by a [4+4] cycloaddition reaction between the compound raw materials containing the conjugated diene group, or may be introduced into the polymer by a polymerization/crosslinking reaction between the reactive groups contained in the compound raw materials containing the [4+4] cycloaddition dynamic covalent bond.

In the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the [2+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond includes, but is not limited to, the action modes of temperature regulation, catalyst addition, illumination, radiation, microwave, etc. For example, the [2+2] cycloaddition dynamic covalent bond can be dissociated by heating at a higher temperature, and then the [2+2] cycloaddition dynamic covalent bond is reformed by heating at a lower temperature; furan and maleimide can carry out a [4+2] cycloaddition reaction at room temperature or under a heating condition to form a dynamic covalent bond, the formed dynamic covalent bond can be dissociated at a temperature higher than 110 ℃, and the dynamic covalent bond can be reformed through cooling. For another example, the [2+2] cycloaddition dynamic covalent bond can be subjected to [2+2] cycloaddition reaction under the long-wavelength light irradiation condition to form a dynamic covalent bond, and then the dynamic covalent bond is dissociated under the short-wavelength light irradiation condition to obtain an unsaturated carbon-carbon double bond again; for example, the cinnamoyl unsaturated carbon-carbon double bond can be subjected to a [2+2] cycloaddition reaction under the ultraviolet irradiation condition that the lambda is more than 280nm to form a dynamic covalent bond, and the bond dissociation is carried out under the ultraviolet irradiation condition that the lambda is less than 280nm to obtain the cinnamoyl unsaturated carbon-carbon double bond again; the coumarin unsaturated carbon-carbon double bond can be subjected to [2+2] cycloaddition reaction under the condition that lambda is larger than 319nm ultraviolet irradiation to form a dynamic covalent bond, and the bond dissociation is carried out under the condition that lambda is smaller than 319nm ultraviolet irradiation to obtain the coumarin unsaturated carbon-carbon double bond again. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction under ultraviolet irradiation at λ 250nm to form a dynamic covalent bond. For another example, anthracene can undergo a [4+4] cycloaddition reaction under uv irradiation at λ 365nm to form a dynamic covalent bond, and then undergo bond dissociation under uv irradiation at λ less than 300 nm. In addition, the [2+2], [4+4] cycloaddition reaction can be carried out under the catalytic condition of a catalyst to form a dynamic covalent bond, wherein the catalyst comprises but is not limited to Lewis acid, Lewis base and metal catalyst; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkylmetal compound, borane, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkylsulfonate, and the like, preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, iron tribromide, iron trichloride, tin tetrachloride, borane, boron trifluoride etherate, scandium trifluoromethanesulfonate; the Lewis bases, which include, but are not limited to, 1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), azacyclocarbene (NHC), quinidine, quinine, etc.; the metal catalyst includes, but is not limited to, catalysts based on iron, cobalt, palladium, ruthenium, nickel, copper, silver, gold, molybdenum, and examples of the metal catalyst used in the present invention for catalyzing the [2+2], [4+4] cycloaddition include, but are not limited to, the following:

in the invention, the dynamic covalent bond of the mercapto-Michael addition can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing the dynamic reversible characteristic; the dynamic covalent mercapto-michael addition bond described in the present invention is selected from at least one of the following structures:

wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group including, but not limited to, aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonate groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein the difference is on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or may be linked to form a ring, the carbon atom being attached to X

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical mercapto-michael addition dynamic covalent bond structures may be exemplified by:

in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the thiol-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, catalyst addition, pH adjustment, and the like. For example, the dissociated mercapto-michael addition dynamic covalent bonds can be regenerated by heating or exchanged to allow the polymer to achieve self-repairability and re-processability. For another example, for a thiol-michael addition dynamic covalent bond, it can be dissociated with a neutral or weakly alkaline solution to be in a dynamic reversible equilibrium. As another example, the presence of a catalyst that promotes the formation and exchange of dynamic covalent bonds, such mercapto-Michael addition reaction catalysts include, but are not limited to, Lewis acids, organophosphates, organo-base catalysts, nucleophilic catalysts, ionic liquid catalysts, and the like; the Lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, etc.; the organic phosphide includes, but is not limited to potassium phosphate, tri-n-propyl phosphine, dimethyl phenyl phosphine, methyl diphenyl phosphine, triphenyl phosphine; organic base catalysts including, but not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, and the like; the nucleophilic catalyst comprises 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylguanidine, 1, 5-diazabicyclo [4, 3, 0] non-5-ene, 1, 8-diazabicyclo [5, 4, 0] -undec-7-ene, 1, 5, 7-triazabicyclo [4, 4, 0] dec-5-ene, 1, 4-diazabicyclo [2, 2, 2] octane, imidazole and 1-methylimidazole; the ionic liquid catalyst includes but is not limited to 1-butyl-3-methylimidazolium hexafluorophosphate, 1- (4-sulfonic) butylpyridine, 1-butyl-3-methylimidazolium tetrahydroborate, 1-allyl-3-methylimidazolium chloride and the like.

In the embodiment of the present invention, the thiol-michael addition dynamic covalent bond may be formed by a thiol-michael addition reaction between a thiol group contained in a compound raw material and a conjugated olefin or a conjugated alkyne, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a thiol-michael addition dynamic covalent bond. Wherein the compound material containing conjugated olefin or conjugated alkyne can be selected from acrolein, acrylic acid, acrylate, propiolate, methacrylate, acrylamide, methacrylamide, acrylonitrile, crotonate, butenedioate, butynedioate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives thereof; among these, the raw material of the compound having a dynamic covalent bond of mercapto-michael addition is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, and an amide having a dynamic covalent bond of mercapto-michael addition are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond of mercapto-michael addition are more preferable.

In the invention, the amine alkene-Michael addition dynamic covalent bond can be activated under a certain condition, and the dissociation, bonding and exchange reaction of bonds occur, thus showing the dynamic reversible characteristic; an amine alkene-michael addition dynamic covalent bond as described in the present invention is selected from the following structures:

wherein the content of the first and second substances,

In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the amine alkene-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, pH adjustment, and the like. For example, for amine alkene-Michael addition dynamic covalent bonds, a weakly acidic (pH 5.3) solution can be used to cause dissociation and thus dynamic reversible equilibrium. As another example, the dissociated amine alkene-Michael addition dynamic covalent bond can be regenerated by heating at 50-100 deg.C or exchanged to allow the polymer to achieve self-repairability and re-processability.

In an embodiment of the present invention, the amine alkene-michael addition dynamic covalent bond may be formed by preparing an intermediate product from terephthalaldehyde, malonic acid, and malonic diester, and reacting the intermediate product with an amino compound through amine alkene-michael addition.

In the invention, the dynamic covalent bond based on triazolinedione-indole can be activated under certain conditions, and the bond dissociation, bonding and exchange reaction occur, so that the dynamic reversible characteristic is embodied; the triazolinedione-indole-based dynamic covalent bond described in the present invention is selected from the following structures:

wherein the content of the first and second substances,

In the embodiment of the present invention, the "certain conditions" for activating the dynamic covalent bond dynamic reversibility based on triazolinedione-indole include, but are not limited to, temperature regulation, pressurization, addition of a catalyst, and the like. For example, the indole and the oxazoline diketone can generate a dynamic covalent bond based on triazoline diketone-indole at the temperature of 0 ℃, the bond dissociation is realized by heating, and the dynamic covalent bond is regenerated by cooling or the exchange of the dynamic covalent bond is carried out, so that the polymer can obtain self-repairability and reprocessing property. For another example, for dynamic covalent bonds based on triazolinedione-indole, they may optionally be dissociated in neutral or slightly alkaline solution to be in dynamic reversible equilibrium. As another example, the presence of a catalyst capable of promoting the formation and exchange of dynamic covalent bonds, said addition reaction catalyst being selected from Lewis acids; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, and the like.

In an embodiment of the present invention, the dynamic covalent bond based on triazolinedione-indole may be formed by an alder-olefin addition reaction between a bisoxazolinedione group and a derivative thereof contained in a compound raw material and indole and a derivative thereof. Wherein the indole or its derivative is selected from indole-3-propionic acid, indole-3-butyric acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, 4- (aminomethyl) indole, 5- (aminomethyl) indole, 3- (2-hydroxyethyl) indole, indole-4-methanol, indole-5-methanol, 3-mercaptoindole, 3-acetylenoindole, 5-amino-2 phenylindole, 2-phenyl-1H-indol-6 amine, 2-phenyl-1H-indol-3-acetaldehyde, (2-phenyl-1H-indol-3-alkyl) carboxylic acid, 6-amino-2-phenyl-1H-indole-3-carboxylic acid ethyl ester Esters, 2- (2-aminophenyl) indole, 2-phenylindole-3-acetonitrile, 4, 6-diamidino-2-phenylindole dihydrochloride, and the like.

In the invention, the dynamic covalent bond based on the dinitrogen heterocarbene can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond are generated, thus showing the dynamic reversible characteristic; the dinitrocarbene-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein the content of the first and second substances,

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; in which, on different carbon atoms

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical bis-azacarbene based dynamic covalent bond structures may be exemplified by:

wherein Me represents a methyl group, Et represents an ethyl group, nBu represents an n-butyl group, Ph represents a phenyl group, and Mes represents a trimethylphenyl group.

In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the double-nitrogen heterocarbene-based dynamic covalent bond include, but are not limited to, temperature regulation, solvent addition and other action modes. For example, the polymer can obtain self-repairability and reworkability by heating the dynamic covalent bond based on the diazacarbone under the temperature condition of higher than 90 ℃ to dissociate the dynamic covalent bond into a diazacarbone structure, and then reducing the temperature to regenerate the dynamic covalent bond or exchange the dynamic covalent bond.

In the embodiment of the invention, the dynamic covalent bond based on the diazacarbone can be formed by utilizing a diazacarbone group contained in a compound raw material or reacting the diazacarbone group with a thiocyano group.

In the invention, the benzoyl-based dynamic covalent bond can be activated under certain conditions and is broken to form a free radical, and the free radical can be reversibly coupled or exchanged to form the dynamic covalent bond again, thereby showing the dynamic reversible characteristic. The benzoyl-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:

wherein each Z is independently selected from a germanium atom or a tin atom; each W is independently selected from an oxygen atom or a sulfur atom, preferably from an oxygen atom;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical benzoyl-based dynamic covalent bond structures may be exemplified by:

in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the benzoyl-based dynamic covalent bond include, but are not limited to, temperature regulation, illumination, radiation, microwave, and the like. For example, the dynamic covalent bond can be broken to form a free radical by heating, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, and the dynamic covalent bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability. The dynamic covalent bond can be broken to form free radicals by illumination, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, the dynamic covalent bond is reformed after the illumination is removed, and the polymer can obtain self-repairability and reprocessing property. The radiation and the microwave can generate free radicals in the system to react with dynamic covalent bonds, so that the self-repairability and the reworkability are obtained.

In the invention, the hexahydrotriazine dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction are carried out, thus showing dynamic reversible characteristics; the "certain condition" for activating the dynamic reversibility of the hexahydrotriazine dynamic covalent bond refers to an appropriate pH condition, heating condition, or the like. The hexahydrotriazine dynamic covalent bond disclosed by the invention is selected from at least one of the following structures:

wherein the content of the first and second substances,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical hexahydrotriazine dynamic covalent bond structures may be mentioned, for example:

in an embodiment of the present invention, the method for performing the process of the sixth aspectThe suitable pH condition for the dynamic reversible reaction of the hydrogen triazine dynamic covalent bond refers to that the dynamic polymer is swelled in a solution with certain pH value or the surface of the dynamic polymer is wetted by the solution with certain pH value, so that the hexahydrotriazine dynamic covalent bond in the dynamic polymer shows dynamic reversibility. For example, hexahydrotriazine dynamic covalent bonds can be dissociated at a pH < 2 and reformed at neutral pH, allowing the polymer to be self-healing and re-processing. Wherein, the acid-base reagent for adjusting pH can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and compounds thereof include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, brilliant carbonate, and potassium tert-butoxide. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, copper acetate, and potassium tert-butoxide are preferable.

In the embodiment of the invention, the hexahydrotriazine dynamic covalent bond can be formed by performing a polycondensation reaction on an amino group and an aldehyde group contained in a compound raw material at a low temperature (such as 50 ℃) to form a hexahydrotriazine dynamic covalent bond of a (I) type, and then heating the hexahydrotriazine dynamic covalent bond of a (II) type at a high temperature (such as 200 ℃); the starting compounds containing hexahydrotriazine dynamic covalent bonds can also be used to introduce polymers by polymerization/crosslinking reactions between the reactive groups they contain. Among these, the starting materials of the hexahydrotriazine compound having a dynamic covalent bond are not particularly limited, and polyols, isocyanates, epoxy compounds, alkenes, alkynes, carboxylic acids, esters, and amides having a dynamic covalent bond of hexahydrotriazine are preferable, and polyols, isocyanates, epoxy compounds, alkenes, alkynes having a dynamic covalent bond of hexahydrotriazine are more preferable.

In the invention, the dynamic exchangeable trialkyl sulfonium bond can be activated under the heating condition and undergoes alkyl exchange reaction, thus showing dynamic reversible characteristics; wherein the "transalkylation reaction" refers to the formation of new trialkylsulfonium bonds elsewhere with concomitant dissociation of old trialkylsulfonium bonds, resulting in exchange of chains and changes in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under the heating conditions of 130-160 ℃. The dynamically exchangeable trialkylsulfonium linkage described in this invention is selected from the following structures:

wherein, X^-Selected from sulfonates, preferably benzenesulfonates, more preferably p-bromobenzenesulfonates;

In the embodiment of the present invention, the dynamically exchangeable trialkylsulfonium bond can be formed by a mercapto-michael addition reaction between a mercapto group contained in a compound raw material and an unsaturated carbon-carbon double bond, and a sulfonate is added as an alkylating agent.

In the present invention, the dynamic acid ester bond is selected from at least one of the following structures:

wherein X is selected from carbon atom or silicon atom; y is selected from titanium atom, aluminum atom, chromium atom, tin atom, zirconium atom, phosphorus atom, preferably titanium atom, aluminum atom, phosphorus atom;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein a represents the number of connections to Y; when Y is selected from aluminum atom, chromium atom and phosphorus atom, a is 2; when Y is selected from titanium atom, tin atom and zirconium atom, a is 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. In the invention, the dynamic acid ester bond is preferably a dynamic titanate bond, a dynamic aluminate bond and a dynamic phosphite bond. Typical dynamic acid ester bond structures may be exemplified by:

in the embodiment of the present invention, the dynamic acid ester bond can be formed by reacting an alcohol or silanol moiety contained in the compound raw material with a corresponding acid or lithium ion hydride or chloride, or can be introduced by using the compound raw material containing the dynamic acid ester bond through a polymerization/crosslinking reaction between reactive groups contained therein.

In the invention, the diketone enamine dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing dynamic reversible characteristics; the diketoenamine dynamic covalent bond described in the present invention is selected from the following structures:

wherein the content of the first and second substances,

In embodiments of the present invention, the "certain conditions" for activating the dynamic covalent bond reversibility of the diketoenamine include, but are not limited to, heating, suitable acidic aqueous conditions, and the like, such that the polymer exhibits good self-healing, recycling and recoverability, stimulus responsiveness, and the like. In the embodiment of the invention, the dynamic covalent bond of the diketone enamine can be dissociated in a strong acid aqueous solution and formed under anhydrous neutral conditions, and the dynamic reversibility can be obtained by adjusting an acid environment because the dynamic covalent bond has good pH stimulus responsiveness. In embodiments of the present invention, acids that may be used to provide the dynamic reaction include, but are not limited to, permanganic acid, hydrochloric acid (hydrochloric acid), sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid, chloric acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation.

In an embodiment of the present invention, the diketone enamine dynamic covalent bond may be formed by reacting 2-acetyl-5, 5-dimethyl-1, 3-cyclohexanedione contained in a compound raw material with an amino compound.

The boron-free dynamic covalent bond contained in the polymer can be kept stable under specific conditions, so that the purposes of providing a balanced structure and mechanical strength are achieved, and dynamic reversibility can be realized under other specific conditions, so that the material can be subjected to complete self-repairing, recycling and plastic deformation; meanwhile, different types of boron-free dynamic covalent bonds exist, so that the polymer can show different response effects to external stimuli such as heat, illumination, pressure, pH, oxidation reduction and the like, and dynamic reversible balance can be promoted or slowed down in a proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.

In order to achieve dynamic reversible equilibrium of boron-free dynamic covalent bonds and thus dynamic reversibility, good dynamic reversible effects are usually achieved by means of temperature adjustment, addition of redox agents, addition of catalysts, light, radiation, microwaves, plasma action, pH adjustment and the like, wherein the temperature adjustment means which can be used in the present invention include, but are not limited to, water bath heating, oil bath heating, electrical heating, microwave heating, laser heating, chemiluminescence, preferably Ultraviolet (UV), Infrared (IR), visible light, laser, and the like, the type of light used in the present invention is not limited, and more preferably, UV, IR, and visible light, the radiation used in the present invention includes, but is not limited to, high-energy ionizing rays such as α rays, β rays, gamma rays, x-rays, electron beams, and the like, the plasma action used in the present invention refers to catalysis using ionized gas-like substances composed of positive and negative ions generated after atoms and atomic groups are ionized, and the microwave used in the present invention refers to electromagnetic waves with a frequency of 300MHz to 300 GHz.

In the present invention, the supramolecular action includes, but is not limited to, the following series: metal-ligand interaction, hydrogen bonding interaction, halogen bonding interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ion interaction (positive and negative ion pair interaction), ion cluster interaction, ion-dipole interaction, dipole-dipole interaction, metallophilic interaction, ionic hydrogen bonding interaction, radical cation dimerization, Lewis acid-base pair interaction, host-guest interaction, phase separation interaction, crystallization interaction.

The supramolecular interaction can be weak dynamic supramolecular interaction which does not dissociate/break in the normal use process of the supramolecular polymer, and the dynamic supramolecular interaction can not dynamically dissociate and generate interconversion dynamic behavior under the conditions of material working temperature, no external field action and the like; or the supermolecule polymer has dynamic strong dynamic supermolecule action in the normal use process, and can generate dynamic dissociation and generate interconversion dynamic behavior under the conditions of material working temperature, no external field action and the like; the working temperature of the material is generally not higher than 60 ℃ and preferably not higher than 25 ℃. Dissociation/fragmentation can also occur under certain conditions, such as weak dynamic supramolecular interactions at high temperatures, strong competitive substances, strong mechanical forces, etc. Where the dynamics of supramolecular interactions refer to the rate of transition between their dissociative and associated/bound states, the faster the rate the more dynamic. The more dynamic supramolecular action is beneficial to obtaining the dilatant effect and the self-repairability, and the less dynamic supramolecular action is beneficial to obtaining the dynamically stable supramolecular polymer.

In an embodiment of the invention, the ligand group in the metal-ligand interaction is selected from cyclopentadiene and a building block comprising at least one coordinating atom. One coordinating atom may form one or more coordination bonds to one or more metal centers (selected from the group consisting of, but not limited to, metal ions, metal centers of metal chelates, metal centers of metal organic compounds, metal centers of metal inorganic compounds), and one metal center may also form one or more coordination bonds to one or more coordinating atoms. The number of coordination bonds formed by a ligand group and a metal center is called the number of teeth of the ligand group, in the embodiment of the present invention, in the same system, a metal center can form a metal-ligand action with one or more of a monodentate ligand, a bidentate ligand, a tridentate ligand and a ligand above a tridentate ligand, and different ligands can also form a ring through the connection of the metal center, so that the present invention can effectively provide strong dynamic and weak dynamic metal-ligand actions with sufficient abundance in types, amounts and performances, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:

wherein X is a coordinating atom or ion, M is a metal center,

is cyclopentadiene ligand, and each ligand group and metal center form an X-M bond as a tooth, wherein, the single bond connects X to indicate that the coordination atoms belong to the same ligand group, when one ligand group contains two or more coordination atoms, X can be the same atom/ion or different atoms/ions, and is selected from but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. In some cases, X is present in the form of negative ions. In the present invention, it is preferred that one coordinating atom form only one coordination bond with one metal center, and therefore the number of coordinating atoms in a ligand group that can form coordination bonds with the same metal center is the number of teeth in the ligand group. The ligand group interacts with the metal-ligand formed by the metal center (as M-L)_mIndicating that L represents a ligand group and m represents the number of ligand groups that interact with the same metal center) is related to the kind and number of coordinating atoms on the ligand group, the kind and valence of the metal center, and the counter ion.

In an embodiment of the invention, one metal center is at least capable of forming a metal-ligand interaction (i.e.M-L) with two parts of said ligand groups in order to be able to form supramolecular cross-linking/polymerization based on metal-ligand interaction₂Structure) unless the metal center is already attached to the polymer; there may also be multiple ligands forming a metal-ligand interaction with the same metal center, where two or more ligand groups may be the same or different. Coordination number of one metal center is limited, coordination atoms of ligand groupsThe more, the fewer the number of ligands that a metal center can coordinate, the lower the degree of supramolecular cross-linking based on metal-ligand interactions; however, since the more the number of teeth each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, it is preferred in the present invention that no more than tridentate ligand groups form a strong dynamic metal-ligand interaction, and that more than tridentate ligand groups form a weak dynamic metal-ligand interaction.

In embodiments of the invention, there may be only one ligand in a supramolecular monomer, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure. One backbone ligand, pendant ligand, and terminal ligand may have the same core ligand structure, which may differ in the point of attachment and/or location of the core ligand structure to a component, such as a polymer chain or small molecule. In the present invention, suitable ligand groups (core ligand structure) can be exemplified as follows, but the present invention is not limited thereto:

examples of monodentate ligand groups are as follows:

bidentate ligand groups are exemplified as follows:

tridentate ligand groups are exemplified below:

tridentate ligand groups are exemplified below:

in embodiments of the invention, polymer chains and/or groups may be grafted at any suitable position of the ligand group (core ligand structure) without affecting the coordination properties.

In embodiments of the present invention, the metal center M may be the metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.

The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).

More preferably, the metal is selected from the group consisting of the first subgroup (Cu, Ag, Au), the second subgroup (Zn, Cd), the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), the lanthanoid group (La, Eu, Tb, Ho, Tm, Lu), and the actinide group (Th). Further preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th are selected to obtain stronger dynamic property.

In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:

other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

In the embodiment of the present invention, the metal inorganic compound is not limited, but oxide or sulfide particles of the above metal, particularly nanoparticles, are preferable.

In embodiments of the present invention, there is also no limitation on the metal chelate that can provide a suitable metal center. Preferably chelates which still have a vacancy in coordination sites, or chelates in which part of the ligands may be replaced by said skeletal ligands of the invention.

In embodiments of the invention, the combination of ligand groups and metal centers is not particularly limited, as long as the ligands are capable of generating a suitable metal-ligand interaction with the metal centers, but the strengths and dynamics of different metal-ligand interactions formed by different metal centers with the same ligand may vary greatly. Some suitable dynamic metal-ligand interaction combinations may be exemplified, but the invention is not limited thereto:

wherein the content of the first and second substances,

each independently represents a link to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain. As will appear again hereinafter

The above definitions and ranges are used, and repeated explanation is omitted unless otherwise specified.

In an embodiment of the invention, the hydrogen bonding in the supramolecular interaction is formed by the interaction of a donor (H, i.e. a hydrogen atom) and an acceptor (Y, i.e. an electronegative atom that accepts a hydrogen atom) of a hydrogen bonding group, which may be of any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by the donor and acceptor of hydrogen bonding groups, and each h. In the following formula, the bonding of the monodentate, bidentate and tridentate hydrogen bonds is schematically illustrated, respectively.

The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:

in the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. The more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. If the number of teeth of the formed hydrogen bond is large, the strength is high, the dynamic property of the hydrogen bond action is weak, and the hydrogen bond can be used as a weak dynamic supermolecule action to play roles in promoting the supermolecule polymer to keep a balanced structure and improving the mechanical properties (modulus and strength). If the number of teeth of the formed hydrogen bond is small, the strength is low, and the dynamics of the hydrogen bonding action is strong, and the dynamics can be provided as the strong dynamic hydrogen bonding action. In embodiments of the invention, it is preferred that no more than four-tooth hydrogen bonds provide strong dynamic supramolecular action, and preferably more than four-tooth hydrogen bonds provide weak dynamic supramolecular action.

In embodiments of the present invention, the hydrogen bonding may be caused by non-covalent interactions between any suitable hydrogen bonding groups, which may comprise only hydrogen bonding donors, or only hydrogen bonding acceptors, or both hydrogen bonding donors and acceptors, preferably both hydrogen bonding groups so that they can independently form hydrogen bonding-preferably comprising at least one of the following structural elements:

in embodiments of the present invention, the strong dynamic hydrogen bonding groups are preferably selected from amide groups, carbamate groups, urea groups, thioamide groups, thiocarbamate groups, thiourea groups, derivatives of the above, and the like.

Examples of the hydrogen bonding group include the following side groups and/or terminal groups, but the present invention is not limited thereto.

Wherein m, n and x are the number of repeating groups, and can be fixed values or average values; m and n are integers with the value range of 0 and more than or equal to 1; the value range of x is an integer greater than or equal to 1.

As examples, hydrogen bonding groups on the backbone of main/side chains (including branched and forked chains) as described below may be mentioned, but the present invention is not limited thereto.

In the embodiment of the present invention, the hydrogen bonding groups forming hydrogen bonding may be complementary combinations of different hydrogen bonding groups or self-complementary combinations of the same hydrogen bonding groups, as long as the groups can form proper hydrogen bonding. Some combinations of hydrogen bonding groups may be exemplified as follows, but the invention is not limited thereto:

in an embodiment of the present invention, the halogen bonding is a non-covalent interaction between a halogen atom and a neutral or negatively charged lewis base, and is essentially an interaction between the sigma-bar orbital of the halogen atom in the halogen bond donor group and an atom or pi-electron system with a lone electron pair in the halogen bond acceptor group. Wherein, the halogen bond donor group can be selected from Cl, Br and I, preferably Br and I; the halogen bond acceptor group may be selected from F, Cl, Br, I, N, O, S, π bonds, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on halogen bond effect, ordered and self-repairing supermolecule polymer can be designed.

In embodiments of the present invention, when a halogen bond is present, the supramolecular monomer may include only a halogen bond donor group or only a halogen bond acceptor group, and may include both donor and acceptor groups. When one of said supramolecular monomers comprises only donor groups or only acceptor groups, said supramolecular polymer further comprises said supramolecular monomers comprising corresponding acceptor groups or donor groups, which interact to form a halogen bond. When both a halogen bond acceptor group and a donor group are included in one of the supramolecular monomers, the positions of the acceptor group and the donor group in the supramolecular monomer are not limited at all.

In embodiments of the present invention, there may be only one halogen bond donor group and/or one halogen bond acceptor group in a supramolecular monomer or a supramolecular polymer, or any suitable combination of multiple halogen bond donor groups and/or halogen bond guest groups may be present simultaneously. The halogen bond donor group and/or the halogen bond acceptor group refer to a core structure. The halo donor groups and/or halo acceptor groups at different positions may have the same core structure, which differs in the point of attachment and/or position of the core structure to the supramolecular monomer.

In the embodiment of the present invention, the combination of atoms forming the halogen bond function is not limited as long as a stable halogen bond function can be formed in the supramolecular polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

-Cl…Cl-、-Cl…F-、-Cl…Br-、-Cl…I-、-Cl…N-、-Cl…O-、-Cl…S-、-Cl…π-、-Br…Br-、-Br…F-、-Br…I-、-Br…N-、-Br…O-、-Br…S-、-Br…π-、-I…I-、-I…F-、-I…N-、-I…O-、-I…S-、-I…π-。

in an embodiment of the invention, the cation-pi interaction is a non-covalent interaction between a cation and a pi-electron system of an aromatic system. The cation-pi action is mainly of three major classes, the first being simple inorganic cations orIon cluster (such as Na)⁺、K⁺、Mg²⁺、NH₄ ⁺、Ca²⁺) And aromatic systems; the second is the interaction between organic cations (e.g., quaternary ammonium cations) and fragrance systems; the third type is the interaction between positively charged atoms in the dipole bond (e.g., H atoms in an N-H bond) and the aromatic system. The cation-pi effect has rich varieties and moderate strength, can stably exist in various environments, and can prepare the supermolecule polymer with rich performance based on the cation-pi effect.

In the embodiment of the present invention, the kind of the cation-pi action is not particularly limited as long as it can form a stable cation-pi action in the supramolecular polymer. Some suitable cationic groups may be exemplified by, but are not limited to:

Na⁺、K⁺、Li⁺、Mg²⁺、Ca²⁺、Be²⁺、H-O、H-S、H-N。

in an embodiment of the invention, the anionic-pi interaction is a non-covalent interaction between an anion and an electron deficient aromatic pi system. The anion may be a simple inorganic non-metallic ion or group of ions (e.g., Cl)^-、Br^-、I^-、OH^-) (ii) a Or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system means that due to different electronegativities of ring-forming atoms, the density distribution of pi electron clouds of rings is not uniform, and pi electrons mainly deviate to the electronegativity high electron direction, so that the density distribution of the pi electron clouds of aromatic rings is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable identification, and can be used for constructing a supramolecular polymer with special performance.

In the embodiment of the present invention, the kind of the anion-pi interaction is not particularly limited as long as it can form a stable anion-pi interaction in the supramolecular polymer. Some suitable anions may be exemplified below, but the invention is not limited thereto:

Cl^-、Br^-、I^-、OH^-、SCN^-；

some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.

In an embodiment of the present invention, the benzene-fluorobenzene reaction is a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon through the combination of dispersion force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The reversibility and stacking effect of the benzene-fluorobenzene action are utilized to prepare the supermolecular polymer with special functions.

In the embodiment of the present invention, the kind of the benzene-fluorobenzene reaction is not limited as long as a stable benzene-fluorobenzene reaction can be formed in the supramolecular polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:

in an embodiment of the present invention, the pi-pi stacking effect is formed by overlapping pi-bonded electron clouds in a supramolecular polymer having a structure capable of providing pi-bonded electron clouds. Pi-pi stacking functions in three ways, including face-to-face stacking, offset stacking, and edge-to-face stacking. The surface accumulation means that the interactive ring surfaces are parallel to each other, the distance between the centers of the parallel ring surfaces is almost equal to the distance between the ring surfaces, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron-withdrawing property of a substituent group connected to the ring surfaces is relatively strong, the pi-pi action of the surface accumulation becomes relatively obvious; the offset accumulation means that the action ring surfaces are parallel to each other, but the center of the ring has certain offset, namely the distance of the center of the ring is larger than the distance between the ring surfaces, the accumulation mode relieves the mutual exclusion action between the two ring surfaces, correspondingly increases the attraction of sigma-pi, and is a common accumulation mode; stacking other than planar stacking and offset stacking is called edge-planar stacking, which has the smallest energy and the smallest intermolecular repulsion, and is often found between ring-conjugated molecules having smaller van der waals surfaces or between ring-conjugated molecules having flexible linkers.

Structures of compounds capable of providing a pi-bonded electron cloud, including but not limited to most condensed cyclic compounds and some heterocyclic compounds with pi-pi conjugation, suitable groups may be exemplified by, but not limited to, the following:

preference is given to

The pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.

In the embodiment of the present invention, the combination of the compounds providing the pi-bonded electron cloud is not particularly limited as long as a suitable pi-pi stacking effect is formed between the compounds. Among them, a combination of an electron-rich compound and an electron-deficient compound is preferable. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in an embodiment of the present invention, the ionic interaction is formed by coulomb force between a positive ionic group and a negative ionic group of at least one pair of oppositely charged ionic groups. The cationic group is an organic group that is relatively receptive to protons, and includes, by way of example and not limitation:

preference is given to

The anion group is an organic group which is relatively easy to lose protons or an inorganic substance with anions, and includes, but is not limited to:

clay (nano) particles with negative ions, preferably

Clay (nano) particles with negative ions. In particular, the cationic group and the anionic group may be in the same supramolecular monomer structure, such as choline glycerophosphate, 2-methacryloyloxyethyl phosphorylcholine, l-carnitine, methacryloylethyl sulfobetaine, and the like. The ionic action can exist stably, and the strength of the ionic action can be well controlled by changing the concentration and the type of the ionic groups.

In the present embodiment, when the ionic interaction exists, the supramolecular monomer may include only a positive ion group, only a negative ion group, only a zwitterion group, and both a positive ion group and a negative ion group. When one of the polymer molecules only contains positive ion groups or only contains negative ion groups, the supramolecular polymer also contains a supramolecular monomer containing corresponding negative ion groups or positive ion groups, and the supramolecular monomer are interacted to form ionic interaction. When both positive and negative ionic groups are contained in one of the supramolecular monomers, the positions of the positive and negative ionic groups in the supramolecular monomer are not limited at all.

In the embodiment of the present invention, the combination of the positive ionic group and the negative ionic group is not particularly limited as long as the positive ionic group can form a suitable ionic action with the negative ionic group. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

and inorganic clay (nano) particles with negative ions.

In the embodiment of the invention, the ion cluster action is formed by aggregating dozens to dozens of pairs of anions and cations. Wherein the anionic group is an organic group which is relatively susceptible to losing a proton, and the cationic group is an organic group which is relatively susceptible to accepting a proton or a metal ion which is relatively susceptible to losing an electron. By way of example, anions that can be incorporated into the polymer include, but are not limited to, negative oxygen ions, carboxylates, sulfonates, phosphates, phosphites, and the like, and counter cations with which cation-anion pairs can be formed include, but are not limited to, alkali metal ions, alkaline earth metal ions, transition metal ions, ammonium, pyridinium, and the like; cations that may be incorporated into the polymer include, but are not limited to, ammonium, pyridinium, and the like, and counter anions with which cation-anion pairs may be formed include, but are not limited to, fluoride, chloride, bromide, iodide, tosylate, and the like. The ion cluster effect has humidity sensitivity, and the counter ions are not directly connected with the polymer, and the strength of the ion cluster effect can be regulated and controlled by changing the quantity and the types of the counter ions and the like.

In the embodiment of the present invention, when the ion cluster effect exists, the cations and anions do not have any limitation on the position in the polymer molecule.

In the embodiment of the present invention, the anion and cation pairs that can form ion clusters are not particularly limited, and some suitable anion and cation pairs may be exemplified as follows, but the present invention is not limited thereto:

in an embodiment of the present invention, the ion-dipole effect is formed by interaction between two atoms with different electronegativities, and when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction of the atom with the greater electronegativity, resulting in asymmetric distribution of electrons and an electric dipole. The ionic group may be any suitable charged organic group, such as the following, but the invention is not limited thereto:

preference is given to

The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-l, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O. The ion-dipole effect can stably exist in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of generating and dissociating the acting force are mild.

In the present embodiment, when the ion-dipole effect exists, the supramolecular monomer may include only an ionic group or only an electric dipole, and may include both an ionic group and an electric dipole. When one of said supramolecular monomers comprises only ionic groups or only electric dipoles, the supramolecular polymer also comprises supramolecular monomers comprising corresponding electric dipoles or ionic groups, which interact to form an ion-dipole effect. When both an ionic group and an electric dipole are included in one of the supramolecular monomers, the positions of the ionic group and the electric dipole in the polymer molecule are not limited at all.

In the embodiment of the present invention, the combination of the ionic group and the electric dipole is not particularly limited as long as the ionic group can form a suitable ion-dipole action with the electric dipole. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

it should be noted that, in the present invention, the ion-dipole effect only refers to the effect between the ionic group and the electric dipole other than the metal-ligand effect, and does not include the metal-ligand effect.

In the embodiment of the present invention, when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction effect of the atom with the larger electronegativity, so that an electric dipole is generated, and the two electric dipoles interact with each other to form a dipole-dipole effect. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C ≡ S, C-S, C-F, C-Cl, C-Br, and C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effects may exhibit differences in dynamics depending on the temperature differences.

In the embodiment of the present invention, the combination between dipoles is not particularly limited as long as a suitable dipole-dipole action can be formed between the dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in an embodiment of the invention, the metalphilic effect is achieved when the two outermost electronic structures are d¹⁰Or d⁸When the metal ions are close to less than the sum of their van der waals radii, an interaction force is generated, and the two metal ions having a metallophilic interaction may be the same or different. The outermost electronic structure is d¹⁰Metal ions of (2) include, but are not limited to, Cu⁺、Ag⁺、Au⁺、Zn²⁺、Hg²⁺、Cd²⁺Preferably of Au⁺、Cd²⁺(ii) a The outermost electronic structure is d⁸Metal ions of (2) include, but are not limited to, Co⁺、Ir⁺、Rh⁺、Ni²⁺、Pt²⁺、Pb²⁺Preferably Pt²⁺、Pb²⁺. The metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the dynamic property of the prepared polymer is more sufficient.

In the embodiment of the present invention, the combination of forming the metallophilic action is not particularly limited as long as a suitable metallophilic action is formed between metal ions. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

Cu-Cu、Ag-Ag、Au-Au、Zn-Zn、Hg-Hg、Cd-Cd、Co-Co、Ir-Ir、Rh-Rh、Ni-Ni、Pt-Pt、Pb-Pb、Cu-Ag、Cu-Au、Ag-Au、Cu-Zn、Cu-Co、Cu-Pt、Zn-Co、Zn-Pt、Co-Pt、Co-Rh、Ni-Pb。

in an embodiment of the present invention, the ionic hydrogen bonding in the supramolecular interaction is composed of a positive ionic group and a negative ionic group capable of forming a hydrogen bonding interaction, and simultaneously forms a hydrogen bonding interaction and a coulomb interaction between positive and negative ions, or is composed of a positive/negative ionic group and a neutral hydrogen bonding group capable of forming a hydrogen bonding interaction, and simultaneously forms a hydrogen bonding interaction and an ion-dipole interaction between the positive/negative ions and the neutral group.

In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:

in the present invention, the building units of the free radical cationic dimerization in the supramolecular interaction are groups containing both a free radical and a cation. By way of example, the free radical cationic dimerization may be formed, including but not limited to the following:

in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:

in the present invention, the lewis acid-base pair effect in the supramolecular interaction refers to a non-covalent interaction formed between a lewis acid and a lewis base. Wherein, the lewis acid refers to a substance (including molecules, ions or atomic groups) capable of accepting an electron pair, and can be selected from positive ion groups (such as alkyl positive ions, nitro positive ions, quaternary ammonium positive ions, imidazole positive ions and the like), metal ions (such as sodium ions, potassium ions, calcium ions, magnesium ions and the like), electron-deficient compounds (such as boron trifluoride, organoborane, aluminum chloride, ferric chloride, sulfur trioxide, dichlorocarbene, trifluoromethanesulfonate and the like), and the lewis acid is preferably alkyl positive ions, quaternary ammonium positive ions, imidazole positive ions, organoborane, and more preferably organoborane; the Lewis base refers to a substance (including a molecule, an ion or an atomic group) capable of giving an electron pair, and can be selected from a group consisting of an anionic group (such as a halide, an oxide, a sulfide, a hydroxide, a carbonate, a nitrate, a sulfate, a phosphate, an alkoxide, an olefin, an aromatic compound, etc.), a compound having a lone pair of electrons (such as ammonia, an amine, an imine, an azo, a nitroso, a cyanogen, an isocyanate, an alcohol, an ether, a thiol, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrous oxide, sulfur dioxide, an organophosphine, a carbene, etc.), preferably an alkoxide, an olefin, an aromatic compound, an amine, an azo, a nitroso, an isocyanate, carbon dioxide, an organophosphine, more preferably an amine, an azo, a nitroso, a compound, An organophosphine.

Wherein, the Lewis acid-base pair action is preferably a 'hindered Lewis acid-base pair action', and the 'hindered Lewis acid-base pair action' means that at least one of Lewis acid and Lewis base in the Lewis acid-base pair action needs to be connected with a 'bulky group with steric effect'; said "bulky group with steric hindrance" may weaken the strength of the coordination bond between the Lewis acid and the Lewis base, thereby allowing the Lewis acid-base pair to exhibit the property of a strong dynamic supramolecule selected from the group consisting of C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl, most preferably from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl. Wherein the azo compound is preferably selected from azomethane, azotert-butane, N-methylazoamidone, N-methylazolylethylamine, N-ethylazolylethylamine, azodiacetic acid, azobenzene, azodiphenylamine, dichloroazobenzene, azobisisobutyronitrileAzodicarbonamide, dimethyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate, di-tert-butyl azodicarboxylate; the nitroso compound is preferably selected from the group consisting of nitrosomethane, nitrosotert-butane, N-nitrosoethanolamine, nitrosobenzene, nitrosotoluene, nitrosochlorobenzene, nitrosonaphthalene, and N-nitrosourea. The Lewis acid-base pair has good dynamic reversibility and can be rapidly dissociated under the condition of slight heating or the existence of an organic solvent, thereby realizing self-repairing or reshaping.

In the embodiment of the present invention, the combination of the formation of the action of the Lewis acid-base pair is not limited as long as a stable Lewis acid-base pair action can be formed in the polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in embodiments of the invention, the host (represented by H) is a compound (macromolecular or infinite organic ionic framework) with a cavity capable of molecular recognition, the guest (represented by G) is a compound (small molecule or ionic group) capable of being recognized by the host and inserted into the cavity of the host, one host molecule can recognize the binding of multiple guest molecules, and in embodiments of the invention, it is preferred that one host molecule recognizes at most two guest molecules, the host molecule includes, but is not limited to, crown ethers, benzocrown ethers, cyclophanes, α -cyclodextrins, β -cyclodextrins, gamma-cyclodextrins, cucurbit [6] ureas, cucurbit [7] ureas, cucurbit [8] ureas, calix [4] arenes, calix [5] arenes, column [6] arenes, column [7] arenes, and some suitable ionic frameworks, preferably crown ethers, β -cyclodextrins, cucurbit [8] ureas, calix [4] arenes, column [5] arenes, long chain heteroaromatics, compounds that can form complexes with moderate ionic bridges, and, heterocyclic compounds that can stabilize the host molecule under moderate, normal conditions, such as long chain cycloolefins, and guest molecules.

In embodiments of the present invention, when a host-guest interaction is present, the supramolecular monomer may include only a host group or only a guest group, or may include both a host group and a guest group. When one of the supramolecular monomers only contains a host group or only a guest group, the supramolecular polymer also contains a corresponding supramolecular monomer, and the host-guest interaction with the supramolecular monomer is strong dynamic and/or weak dynamic. When both a host group and a guest group are contained in one of the supramolecular monomers, the positions of the host group and the guest group in the supramolecular monomer are not limited.

In embodiments of the present invention, there may be only one host group and/or one guest group in a supramolecular monomer or a supramolecular polymer, or any suitable combination of multiple host groups and/or guest groups may be present simultaneously. A host group and/or guest group refers to a core structure. Host groups and/or guest groups at different positions may have the same core structure, which differs in the point of attachment and/or position of the core structure to a component, such as a polymer chain or small molecule.

Suitable host groups may be exemplified by, but are not limited to:

suitable guest groups may be exemplified by, but are not limited to:

in the embodiment of the present invention, the combination of the host group and the guest group is not particularly limited as long as the host can form a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the embodiments of the present invention, the phase separation refers to that polymer segments with different chemical compositions form incompatible phases respectively due to incompatibility or compatibility with the environment. In the present invention, phase separation effects include, but are not limited to, phase separation caused by incompatible polymer block structures in the block polymer supramolecular monomers and phase separation caused by other supramolecular effects, preferably phase separation caused by incompatible polymer block structures in the block polymer supramolecular monomers. Among them, the crystallization in the present invention refers to an ordered region in which a part of polymer segments can be arranged to form a different phase by separating from other polymer segments in an amorphous state. Crystallization is also a particular phase separation. In the present invention, the crystallization includes, but is not limited to, crystallization due to the regularity easy-to-crystallize block in the block polymer supramolecular monomer and crystallization due to liquid crystal and other supramolecular effects, and preferably, crystallization due to the regularity easy-to-crystallize block in the block polymer supramolecular monomer and crystallization due to liquid crystal.

The block structure capable of forming phase separation and/or crystallization in the present invention refers to a block polymer supramolecular monomer with a block structure, wherein the total number of blocks is 2 or more, and at least two blocks can form mutually incompatible phases, that is, when only two blocks are contained, the two blocks form mutually incompatible phases; when three and three blocks are present, the remaining blocks may form compatible or incompatible phases with the other blocks, except that at least two of the blocks may form incompatible phases.

In a preferred embodiment of the present invention, it is preferred that the block polymeric supramolecular monomer comprises at least one hard segment and at least one soft segment. Wherein the hard segments are intermixed with each other and/or independently form a crystalline phase and/or a phase incompatible with the soft segments to form phase-separated physical polymerization and/or crosslinking based on the hard segments; the phase formed by each soft segment is in an amorphous state. The hard segment-based physical polymerization/crosslinking results in polymers with similar physical properties after covalent polymerization/crosslinking, including but not limited to, increased apparent molecular weight, elasticity, dimensional stability, and enhanced mechanical strength. Hard segment phase-separated physical crosslinking is particularly suitable for providing the equilibrium structure, i.e. dimensional stability, of the polymers of the present invention. Of these, it is more preferable that at least two hard segments are contained and connected to each other by a soft segment, that is, at least two hard segments and at least one soft segment form an alternating hard segment-soft segment structure to form phase-separated physical crosslinks based on the hard segments, and crystallization/phase separation of the hard segments will more effectively form inter-chain phase-separated physical crosslinks, which can effectively provide the strength of the phase-separated physical crosslinks, the equilibrium structure of the polymer, and the mechanical properties of the physically phase-separated polymer.

In another preferred embodiment of the present invention, it is preferred that the block polymeric supramolecular monomers are amphiphilic polymeric molecules containing at least one solenophilic segment and at least one solenophilic segment; more preferably at least two solvophobic segments and linked to each other by a solvophilic segment, i.e. at least two solvophobic segments and at least one solvophilic segment forming an alternating solvophobic segment-solvophilic segment structure to form a polymer gel.

In the embodiment of the present invention, the chain topology of the block polymer supramolecular monomer is not particularly limited, and may be a linear structure, a branched structure, a cyclic structure, a cluster structure, a crosslinked particle, and a combination of two or more thereof, preferably a linear structure and a branched structure. When a branched structure is present, part of the hard/soft segments may be on the main chain and part of the hard/soft segments may be on the side chains/branches/bifurcations.

In the embodiment of the present invention, in the block polymer supramolecular monomer having both hard segments and soft segments, each hard segment may be the same or different, and each soft segment may be the same or different; wherein, the hard segment and the soft segment can respectively and independently comprise two or more than two same or different sub-segments; the sub-chain segments can be smaller chain segments on the same main chain or smaller chain segments on side chains, branched chains and branched chains; such differences include, but are not limited to, differences in chemical composition, differences in molecular weight, differences in topology, and differences in spatial configuration. In the embodiment of the present invention, each of the hard segment, the soft segment and the sub-segment thereof may be a homopolymer segment, a copolymer segment, a homopolymeric cluster or a copolymeric cluster, a crosslinked particle having a gel point of homo-polymerization or copolymerization or a functional group, or any combination of the foregoing.

In the embodiment of the present invention, the topology of any segment in the hard segment is not particularly limited, and may be a linear structure, a branched structure, a cyclic structure, a cluster structure, a crosslinked particle structure, and a combination of two or more thereof, preferably a linear and a branched structure. The topology of any segment in the soft segment is not particularly limited, and may be a linear structure, a branched structure, a cyclic structure, a cluster structure, a cross-linked particle structure, or a combination of two or more thereof, preferably a linear, branched, and cluster structure.

In an embodiment of the invention, the different blocks are linked to each other at least by one covalent bond or by a weak dynamic supramolecular interaction formed by a pair of supramolecular groups/units, preferably by one covalent bond. Wherein said covalent linking may be the presence of a linker having a chemical structure different from that of the segment to be linked, said linker having a molecular weight not higher than 1000Da, preferably the number of carbon atoms of the linker is not higher than 20, more preferably not higher than 10.

Some preferred structures of the block polymer supramolecular monomer of the present invention shown in the following formulas (a) to (e) can be exemplified by the block polymer supramolecular monomer having only two blocks of block a and block B, but the present invention is not limited thereto:

wherein, formula (a) is a linear structure, n is the number of alternating units of A type block-B type block, and is more than or equal to 0; preferably n is greater than or equal to 1; the formula (B) is a linear structure, the two end sections are A type blocks, n is the number of alternating units of the A type block and the B type block, and the number is more than or equal to 0; wherein one preferred structure is that A is a hard segment/solvophobic segment, and n is 0; wherein, another preferred structure is that B is a hard segment/solvophobic segment, and n is more than or equal to 1; formula (c) is a branched structure, x is the number of A-type block branching units attached to the B-type block B; n is the number of alternating units of block type A-block type B, which is greater than or equal to 0; y is the number of A-type block-B-type block branching units linked to B-type block B; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3; formula (d) is a branched structure, x is the number of A-type block branching units attached to the B-type block B; n is the number of alternating units of block type A-block type B, which is greater than or equal to 0; y is the number of branching units that link the A-type blocks alternating with the B-type blocks and end capped with the A-type blocks; x and y are more than or equal to 0, and the sum of x and y is more than or equal to 3; wherein, one preferred structure is that A is a hard segment/solvophobic segment, n is 0, and the sum of x and y is more than or equal to 3; wherein, another preferred structure is that B is a hard segment/solvophobic segment, n is more than or equal to 1, and the sum of x and y is more than or equal to 3; formula (e) is a cyclic structure, n is the number of alternating units of type A block-type B block, which is greater than or equal to 1; preferably, n is 2 or more. Among them, more preferred are the case where A in the formula (b) is a hard segment/solvophobic segment and n is 0, and the case where A in the formula (d) is a hard segment/solvophobic segment and n is 0 and the sum of x and y is 3 or more.

Furthermore, the structure of the block polymeric supramolecular monomers of the present invention may also be any combination of the preferred structures listed above and any other suitable structure, which one skilled in the art can reasonably realize in accordance with the logic and context of the present invention.

In the present invention, the hard segment generally has a higher glass transition temperature and/or forms a crystalline phase and/or forms a phase which is more thermally stable and/or has a higher mechanical strength and/or is less soluble than the soft segment does. In an embodiment of the present invention, a two-phase structure of a soft phase consisting of soft segments and a hard phase consisting of hard segments is generally present in the supramolecular polymer comprising phase separation and/or crystallization; however, the different hard phases formed by the different hard segments may also be incompatible, as may the different soft phases formed by the different soft segments, i.e. two or even three or more incompatible phases (hereinafter referred to as "heterogeneous supramolecular polymers") may be present in the supramolecular polymer comprising phase separation and/or crystallization. In the embodiment of the present invention, the phase topology (phase morphology) formed by the soft phase composed of soft segments and the hard phase composed of hard segments is not limited, and includes, but is not limited to, a sphere, a cylinder, a spiral, a layer, and a combination thereof. Any phase, including different soft phases and different hard phases, can be dispersed in another phase, can form interpenetrating double/multiple continuous phases with other phases, and can be mutually independent continuous phases. In the embodiment of the present invention, it is preferable that the soft phase is a continuous phase, the hard phase is a discontinuous phase dispersed in the soft phase, and it is more preferable that the hard phase is dispersed in the soft phase in a spherical shape, so that the multi-phase supramolecular polymer can more conveniently have better flexibility and elasticity and be more suitable for dynamic properties of other supramolecular functions. The size of the discontinuous hard phase is typically no greater than 100 microns, more preferably no greater than 10 microns, more preferably no greater than 1 micron, and most preferably no greater than 100 nanometers. The total content of hard segments of the dynamic polymer is not particularly limited, and preferably ranges from 1% to 50% by total weight, more preferably from 5% to 35% by total weight, to facilitate the formation of effective phase separation and/or crystalline crosslinks.

In embodiments of the invention, the degree of crosslinking of the phase-separated and/or crystalline crosslinks formed by the hard segments may be above or below their gel point. When the degree of crosslinking of the phase separation and/or crystalline crosslinks formed by the hard segments is at the gel point (including the gel point, the same applies hereinafter), a three-dimensional infinite network based entirely on phase separation and/or crystalline crosslinks can be obtained, and in the case of complete dissociation of other supramolecular interactions, the heterogeneous supramolecular polymer can also maintain an equilibrium structure, i.e. dimensional stability; when the phase separation and/or the degree of crosslinking of the crystalline crosslinks formed by the hard segments is at their gel point, the heterogeneous supramolecular polymer is also dissociated with complete dissociation of the other supramolecular interactions.

In the embodiment of the present invention, the chemical composition of the hard segment is not particularly limited, and may be selected from, but not limited to, polymer segments whose main chain is a carbon chain structure, a carbon hetero chain structure, a carbon element chain structure, an element hetero chain structure, a carbon hetero element chain structure, and other supramolecular interaction units. The carbon chain structure is a structure of which the main chain skeleton only contains carbon atoms; the carbon heterochain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms and any one or more heteroatoms, wherein the heteroatoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure that a main chain skeleton simultaneously contains carbon atoms and any one or more element atoms, wherein the element atoms comprise but are not limited to silicon, boron and aluminum; the element chain structure is a structure that a main chain skeleton only contains element atoms; the element heterochain structure is a structure which has a main chain skeleton and only contains at least one heteroatom and at least one element atom; the carbon-heteroatom chain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms, heteroatoms and element atoms. Among them, a carbon chain structure and a carbon-hetero chain structure are preferable because the raw materials are easily available and the industrial preparation technology is mature. By way of example, the hard segment of the polymer may be a segment based on, but not limited to, the following polymer segments, groups, or any combination thereof: amorphous polymer segments with high glass transition temperatures, such as polystyrene, polyvinylpyridine, hydrogenated polynorbornene, polyetheretherketone, polyaromatic carbonates, polysulfones, and the like; polymer chain segments rich in rigid conjugated structures, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, polythiophene and the like; polymer segments rich in crystalline phases, groups such as crystalline polyethylene, crystalline polypropylene, crystalline polyesters, crystalline polyethers, liquid crystal polymers (such as polyterephthalamide, polybenzothiazole, polybenzoxazole, etc.), liquid crystal groups (such as azobenzene and its derivatives, biphenyl, diphenyl terephthalate, cholesteric derivatives, etc.). The term "crystallization" as used herein refers to a process in which polymer chains are arranged to form ordered domains, and includes crystallization caused by a supramolecular interaction such as coordination, complexation, assembly, association, or aggregation, crystallization caused by an incompatible phase, crystallization caused by an incompatible block structure, crystallization caused by a regular easily-crystallized segment, crystallization caused by a liquid crystal, and the like. Among them, it is preferable to introduce a liquid crystal segment and use crystallization caused by liquid crystal, because crystallization can be effectively controlled and controlled, and dynamic reversible transformation can be realized under the stimulation conditions of heat, light, pH, chemical change, and the like.

In the embodiment of the present invention, the soft segment polymer skeleton may be selected from, but not limited to, polymer chain segments whose main chains are carbon chain structures, carbon hetero chain structures, carbon element chain structures, element hetero chain structures, and carbon hetero element chain structures, and may also be other supramolecular acting units, preferably carbon chain structures, carbon hetero chain structures, element hetero chain structures, and carbon hetero element chain structures, because of their readily available raw materials and mature preparation technology. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: a homopolymer or a copolymer of an acrylate polymer, a saturated olefin polymer, an unsaturated olefin polymer, a halogen-containing olefin polymer, a silicone polymer, a polyether polymer, a polyester polymer, a bio-polyester polymer, or the like.

In an embodiment of the present invention, the hard phase of the multi-phase supramolecular polymer may have no glass transition temperature, or one or more glass transition temperatures, and may also have one or more phase-splitting physical cross-linking temperatures, preferably the phase-splitting physical cross-linking temperature of any hard segment is higher than the upper limit of the working temperature range; the soft phase of the heterogeneous supramolecular polymer may also have no glass transition temperature, or one or more glass transition temperatures, preferably at least one of which is not higher than the lower limit of the working temperature range; when the multiphase supramolecular polymer contains auxiliary agents or fillers such as plasticizers and the like, so that at least one glass transition temperature of a soft segment of the multiphase supramolecular polymer is not higher than the lower limit of a working temperature range, and the decrosslinking temperature of a hard segment is higher than the upper limit of the working temperature range, the composition also belongs to the multiphase supramolecular polymer.

In an embodiment of the present invention, the block polymer supramolecular monomer may simultaneously contain other supramolecular groups/units. The positions of the other supramolecular groups/units are not limited, and the other supramolecular groups/units can be positioned at the joints of the hard segments and/or the soft segments, and can be selectively positioned at the joints of the soft segment main chain framework and/or the soft segment side groups and/or the soft segment end groups and/or the soft segments and the hard segments of the block polymer supramolecular monomer, particularly the soft segment side chain framework/side group/end group is more favorable for embodying the dynamic property of other supramolecular action.

In the present invention, the term "dilatancy" may also be referred to as shear thickening, and refers to the property of a material that, under the action of shear forces or other mechanical external forces, the viscosity and/or strength and/or hardness of the material increases with increasing rate of action of the force, the material exhibiting viscous flow at lower rates of action of the force but exhibiting higher viscosity at higher rates of action of the force and a change in character such that it has a temporary rigidity; after the stress is removed, the material returns to its normal viscous state.

In the present invention, the dilatancy includes, but is not limited to, dilatancy through vitrification, dynamic dilatancy, entanglement dilatancy, dispersive dilatancy, aerodynamic dilatancy and physical mixtures thereof, chemical hybrids and combinations of the two. Wherein, the dynamic dilatancy is preferably realized by introducing strong dynamic supramolecules and/or strong dynamic covalent bonds into the structure of the polymer per se and utilizing the change of the strong dynamic supramolecules and/or the strong dynamic covalent bonds under the shearing action; the glass-transition dilatancy is realized by the glass transition of chain segments in the structure of the polymer; the entanglement dilatancy is realized by utilizing the fact that polymer chains cannot move in time under the shearing action caused by molecular chain entanglement; the dispersivity dilatancy is realized by dispersing a dispersion liquid of solid microparticles in a dispersion medium and by cluster effect/fluidity of the dispersion liquid under shearing action; the aerodynamic dilatancy is achieved by regulating the cell structure of the polymer foam, which is predominantly closed-cell but contains small-sized open cells, so that when the foam is compressed or flushed back, gas is slowly released or admitted and thus exhibits dilatancy characteristics. In the embodiment of the present invention, the other dilatancy component is not limited thereto.

Wherein, the physical mixing form is that the dilatant polymer/dilatant composition/dilatant structure in different modes are mixed together in a physical blending form to realize the dilatancy of the matrix, and the components in the system are independent of each other; wherein, the chemical hybridization forms, namely different modes of dilatant polymer/dilatant composition/dilatant structure exist in the same polymer chain or the same polymer network at the same time, and are connected with each other in a chemical mode (including covalent bond, ionic bond, metallic bond, supermolecule action and the like). By way of suitable example, the dilatancy may be achieved by methods including, but not limited to, the following: such as mixing of a glassy dilatant polymer with a dynamic dilatant polymer, mixing of a glassy dilatant polymer with a dispersive dilatant composition, mixing of a glassy dilatant polymer with a pneumatic dilatant structure, mixing of a glassy dilatant polymer with a dynamic dilatant polymer with a dispersive dilatant composition, mixing of a glassy dilatant polymer with a dynamic dilatant polymer and a dynamic dilatant composition and then combining with a pneumatic dilatant structure, mixing of a glassy dilatant polymer with a dispersive dilatant composition and then combining with a pneumatic dilatant structure, mixing of a glassy dilatant polymer with a dynamic dilatant polymer and a dispersive dilatant composition and then combining with a pneumatic dilatant structure, chemical hybrid forms of both a glassy dilatant polymer and a dynamic dilatant polymer on a polymer chain and chemical hybrid forms of both a glassy dilatant polymer and a dynamic dilatant polymer and a dispersive dilatant polymer on a polymer chain Other forms of mixing/combining. When the intrinsic dilatancy polymer is physically mixed to realize dilatancy, the content of the dynamic dilatancy polymer in the composition of the intrinsic dilatancy polymer is preferably 30-80%, and the content of the vitreous dilatancy polymer is preferably 20-70%; the content of the dynamic dilatant polymer is more preferably 50 to 70%, and the content of the vitreous dilatant polymer is more preferably 30 to 50%.

In the present invention, the dilatant polymer (composition), when it is in the state of an elastomer, gel or fluid, preferably has a ball rebound of less than 80%, more preferably a rebound of less than 50%, even more preferably less than 25%, even more preferably less than 10%, wherein the test method is ASTM D-2632 "Rubber Property-Resilience by vertical rebound" (ASTM D-2632 "Rubber Property-vertical rebound"); when the foam is in its state, it preferably has a ball rebound of less than 50%, more preferably less than 25%, more preferably less than 10%, still more preferably less than 5%, wherein the Test method is ASTM D-3574H "Flexible Cellular Materials Slab, bound and Molded urethane foams, Test H, Resilience (ball rebound) Test" (ASTM D-3574H, "Flexible Cellular Material-Panel, Bonded and Molded polyurethane foam, Test H, rebound (ball rebound) Test").

In the present invention, the springback ratio is a ratio of a springback height to a drop height of a steel ball having a predetermined mass and shape dropped on a sample surface. That is, a steel ball with a specified mass and shape is dropped onto the surface of a sample from a fixed height, the rebound height of the steel ball is measured, and the percentage of the ratio of the rebound height (denoted as H) to the drop height (denoted as H) is calculated as the rebound ratio (denoted as R) of the sample, which can be calculated by the following formula:

the rebound resilience R is H/H100 percent;

wherein h is the rebound height in millimeters (mm);

where H is the drop height in millimeters (mm).

In the present invention, the intrinsic dilatant polymer (composition) may exhibit creep or slow rebound characteristics under specific conditions, i.e., the polymer deforms when subjected to an external force; and after the external force is removed, the material can not rebound or can not immediately rebound/recover the deformation but slowly rebound/recover the deformation. In the present invention, composites containing an intrinsically dilatant polymer may still exhibit dilatancy but may not exhibit creep or slow rebound characteristics, or have lower creep or slow rebound characteristics, or have only high resilience, by compounding with non-dilatant polymers and/or fillers and the like and/or network interpenetration and the like. The polymer composite containing the dispersion may also have dilatancy but may not exhibit creep or slow rebound characteristics, or have lower creep or slow rebound characteristics, or only high rebound. The polymer composition containing the dispersion may also have dilatancy but may not exhibit creep or slow rebound characteristics, or have lower creep or slow rebound characteristics, or only high rebound. The polymers (compositions) containing aerodynamic dilatant structures all have slow rebound resilience.

In the present invention, the rebound time of the resilient dilatant polymer (composition) at normal temperature and pressure is not particularly limited, but is preferably 2 seconds to 120 seconds, more preferably 5 seconds to 60 seconds, and further preferably 7 seconds to 30 seconds. Wherein, the rebound time refers to the time required for basically restoring the sample after applying the indentation force to the sample to generate the specified deformation and keeping the specified time. When the polymer is in the form of an elastomer or gel, the polymer is pressed into the sample by 40% of the initial thickness of the sample under pressure, the sample is kept for 60 seconds, and the time required for the sample to recover to a deformation position with the initial thickness of 3% is measured and recorded as the rebound time of the sample; when the polymer is in the form of a foam, it is pressed into the sample at 75% of its original thickness under pressure for 60 seconds, and the time required for the sample to return to the deformed position at 5% of its original thickness is measured and recorded as its spring back time.

In the present invention, the "vitreous dilatancy" refers to the dilatancy achieved by the glass transition of segments in the structure of the polymer itself. The glass dilatant polymer has one or more glass transition temperatures, and the soft segment has at least one glass transition temperature of-40 ℃ to 60 ℃, and has dilatancy mainly caused by the glass transition temperature. In the present invention, the glass transition temperature is one of the requirements for achieving the dilatancy of the vitrified dilatant polymer, that is, the dilatancy utilizes at least the glass transition of the polymer, particularly the glass transition of the soft segment structure thereof. The glass transition temperature refers to a transition temperature at which a polymer is transformed from a brittle glass state to an elastic rubbery state, that is, a temperature at which a glass transition occurs, and may be a temperature point or a temperature range (also referred to as a glass transition region). When the temperature of the polymer drops below its Tg, the polymer segments are frozen and appear brittle; as the temperature of the polymer increases and exceeds its Tg, the polymer segments move, soften, and exhibit an elastic rubbery state; in the vicinity of Tg, the polymer softens by the movement of polymer segments therein, exhibits good viscoelasticity, and thus obtains dilatant properties. When the Tg of the polymer is near room temperature, the polymer shows room temperature dilatancy, namely, the dilatancy can be maximized by regulating the glass transition temperature of the polymer to be near room temperature.

In the present invention, the glass transition temperature (Tg) of the vitrification dilatant polymer can be measured by a known test method by those skilled in the art. At least the glass transition temperature can be measured by a method commonly used in the art, such as Differential Scanning Calorimetry (DSC), dynamic mechanical analysis/Dynamic Mechanical Analysis (DMA), and dynamic mechanical thermal analysis/Dynamic Mechanical Thermal Analysis (DMTA), for example.

In the present invention, the temperature range (temperature span) of the glass transition temperature is not particularly limited. When the glass transition temperature has a wide temperature range, the polymer can realize viscoelastic transition in the wide temperature range, so that a wide rebound temperature range is obtained, the temperature sensitivity of the polymer is reduced, and the problem of polymer hardening (namely, the low-temperature hardening problem) caused by temperature reduction can be avoided to a certain extent; when the glass transition temperature has a narrow temperature range, the rebound temperature range of the polymer is narrow, the temperature controllability of the rebound process is better, and the temperature dependence is higher.

In the invention, the glass transition temperature of the polymer can be regulated and controlled by regulating and controlling the chemical composition and topological structure of the soft segment of the vitrification dilatant polymer, so that the glass transition temperature is close to the use temperature of the dilatant material, and the maximized dilatant property is obtained.

In the embodiment of the present invention, the chemical composition of the soft segment and/or the segment between crosslinking points of the vitrification dilatant polymer is not particularly limited, but is selected from, but not limited to, polymer segments whose main chain is a carbon chain structure, a carbon hetero chain structure, an elemental organic chain structure, and a carbon hetero element chain structure, and preferably a carbon chain structure, a carbon hetero chain structure, and an elemental organic chain structure, depending on the temperature range of use thereof, because the raw materials are easily available and the preparation technique is mature. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: acrylic polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, polyether polymers, polyester polymers, biopolyester polymers, epoxy polymers, polythioether polymers, silicone polymers, and the like, and homopolymers, copolymers, modifications, derivatives, and the like of the above polymers; preferred are unsaturated olefin polymers, polyether polymers, epoxy polymers, polysulfide polymers, polyorganosiloxane polymers, and homopolymers, copolymers, modified products, and derivatives of the above polymers. Preferably, the soft segment polymer chain backbone may be a segment based on the following polymers, but the present invention is not limited thereto: polyethylene, polyvinyl acetate, polyethylacrylate, polybutyl acrylate, polyoctyl acrylate, polyvinylmethylether, polyvinylethylether, ethylene-propylene copolymer, polyisobutylene, polychloroprene, poly cis-1, 4-isoprene, poly trans-1, 4-isoprene, styrene-butadiene copolymer, polynorbornene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, ethylene oxide-propylene oxide copolymer (such as polyethylene oxide-polypropylene oxide copolymer), polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, hydrogenpolysiloxane, and the like, and homopolymers, copolymers, modifications, derivatives, and the like of the polymers. Segments with different glass transition temperatures can achieve a vitrification dilatancy at different temperatures, so that the corresponding material can use its vitrification dilatancy in different temperature ranges.

In the embodiment of the present invention, the molecular weight of the soft segment of the vitrification dilatant polymer is not particularly limited, and it may be a macromolecular segment having a molecular weight of more than 1000Da, or an oligomer or a small molecular segment having a molecular weight of less than 1000 Da.

In an embodiment of the present invention, the topology of the soft segment of the vitrified dilatant polymer is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure (including, but not limited to, star, H, dendritic, comb, hyperbranched), a cyclic structure (including, but not limited to, a single ring, multiple rings, bridged rings, grommets, torus), a two-dimensional/three-dimensional cluster structure, and a combination of two or any of them; among them, a linear structure and a branched structure are preferable. The linear chain structure has a simple structure, is easy to regulate, synthesize and control the structure, and is easy to obtain a single glass transition temperature or a glass transition region with a narrow temperature range, so that the dilatancy of the polymer and the dependence and responsiveness on the environmental temperature are improved. The branched structure contains side chains, branched chains and the like, so that the glass transition temperature of the polymer is easily reduced and regulated, and the low-temperature resilience is improved.

In the invention, the working temperature range of the vitrifying dilatancy caused by polymer vitrification can be designed and selected according to proper polymer chain segments or the composition thereof, so that the characteristic of strong controllability is achieved, and the dilatancy material with a specific working temperature interval can be conveniently obtained.

In the present invention, the "dynamic dilatancy" is preferably achieved by introducing strong dynamic supramolecular action and/or strong dynamic covalent bond into the structure of the polymer itself, and by utilizing the change of the strong dynamic property of the strong dynamic supramolecular action and/or the strong dynamic covalent bond under shearing action. The dynamic dilatant polymer contains at least one of strong dynamic supermolecular action and strong dynamic covalent bond in the polymer. Furthermore, dynamic dilatancy also includes the formation of molecules based on strong dynamic covalent bonds and/or strong dynamic supramolecular interactions between inorganic/organic particles and between polymers/small molecules etc.

In the present invention, typical strong dynamic covalent bonds include, but are not limited to: boron-containing dynamic covalent bonds, dynamic acid ester bonds, dynamic covalent bonds based on reversible radicals, more preferably saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds (especially saturated five-membered ring organic borate bonds/unsaturated five-membered ring organic borate bonds/saturated six-membered ring organic borate bonds/unsaturated six-membered ring organic borate bonds with aminomethyl benzene groups), inorganic boronic acid monoester bonds, organic boronic acid monoester bonds, inorganic boronic acid silicone bonds, organic boronic acid silicone bonds, dynamic titanate silicone bonds; typical strong dynamic supramolecular interactions include, but are not limited to: a monodentate hydrogen bonding action, a bidentate hydrogen bonding action, a monodentate metal-ligand action, a bidentate metal-ligand action, an ionic clustering action, an ion-dipole action, a host-guest action, a metallophilic action, a dipole-dipole action, a halogen bonding action, a lewis acid-base pair action, a cation-pi action, an anion-pi action, a benzene-fluorobenzene action, a pi-pi stacking action, an ionic hydrogen bonding action, a radical cation dimerization action, more preferably a monodentate hydrogen bonding action, a bidentate hydrogen bonding action, a monodentate metal-ligand action, an ionic action, an ion-dipole action, a host-guest action, an ionic hydrogen bonding action.

In the embodiment of the present invention, when the group constituting strong dynamics in the dynamic dilatant polymer is located at the terminal group, pendant group or side chain of a general covalent cross-linked network/dynamic covalent cross-linked network/supramolecular interaction cross-linked network, or is present in the form of a dispersion in a polymer structure having a balanced structure, the polymer can have good dynamics/dilatant properties and a balanced structure, giving better direct usability.

In the present invention, the dynamic exchange rate is preferably 100000-0.0001s for the strong dynamic covalent bonds and the strong dynamic supramolecular interactions described in the dynamic dilatant polymer^-1The amount of the surfactant is preferably 1000-0.001s as required according to different performance requirements and application occasions^-1Preferably in the range of 100 to 0.01s^-1It is also preferably 10 to 0.1s^-1. Different dynamic exchange rates are combined with different polymer structures, such as cross-linking degree, polymer chain topological structure, cross-linked network topological structure, glass transition temperature, composite structure and the like, so that different force action response rates can be provided, different viscosity-elasticity transformation or elasticity enhancement can be generated, and different energy absorption effects and rebound responses can be generated. The technical scheme of the invention can skillfully and effectively design and regulate the dynamic dilatancy by designing and selecting proper dynamic units and polymer structures so as to meet the requirements of different performances in different occasions to the maximum extent. For example, higher rates may meet higher cushioning requirements for older shoes, lower rates may meet the requirements for both high rebound and cushioning for sprints, jumps, etc., lower rates may meet low creep requirements for shock absorption for precision instruments, and so forth.

In the invention, the dynamic dilatancy caused by the strong dynamic supermolecule effect and/or dynamic covalent bond has the characteristics of rich regulation and control means, high dynamic transformation speed and the like.

In the present invention, the chemical composition of the soft segment and/or the segment between the crosslinking points of the dynamic dilatant polymer is not particularly limited, but depends on the temperature range of use, and is selected from, but not limited to, polymer segments having a main chain of a carbon chain structure, a carbon hetero chain structure, an elemental organic chain structure, and a carbon hetero element chain structure, and preferably a carbon chain structure, a carbon hetero chain structure, and an elemental organic chain structure, because the raw materials are easily available and the production technique is mature. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modifications, derivatives and the like of acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, polyether polymers, polyester polymers, biopolyester polymers, epoxy polymers, polythioether polymers, silicone polymers and the like; preferred are homopolymers, copolymers, modified products, derivatives and the like of unsaturated olefin polymers, polyether polymers, epoxy polymers, polysulfide polymers, polyorganosiloxane polymers and the like. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modifications, and derivatives of polyethylene, polyvinyl acetate, polyethylacrylate, polybutylacrylate, polyoctyl acrylate, polyvinylmethylether, polyvinylethylether, ethylene-propylene copolymer, polyisobutylene, polychloroprene, poly cis-1, 4-isoprene, poly trans-1, 4-isoprene, styrene-butadiene copolymer, polynorbornene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, ethylene oxide-propylene oxide copolymer (such as polyethylene oxide-polypropylene oxide copolymer), polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, and hydrogenpolysiloxane. Preferably having a low glass transition temperature, preferably no higher than 25 c, more preferably no higher than 0 c, more preferably no higher than-40 c, more preferably no higher than-100 c, in order to have a wide temperature range for use, i.e. to be able to be used at low temperatures (e.g. north) and high temperatures (e.g. south).

In the invention, the entanglement dilatancy is realized by utilizing the fact that polymer chains cannot move in time when the polymer chains are sheared due to molecular chain entanglement. Preferably, the glass transition temperature of the molecular chain of the polymer is not higher than-20 ℃, more preferably not higher than-40 ℃, more preferably not higher than-60 ℃, more preferably not higher than-100 ℃; the molecular weight thereof needs to be high enough to obtain entanglement under shear, and is preferably not less than 100kDa, more preferably not less than 1000 kDa.

In the present invention, the dispersive dilatancy composition at least contains solid microparticles and a dispersion medium, wherein the volume fraction of the solid microparticles is preferably not less than 20%, more preferably not less than 30%, and more preferably not less than 40%.

Wherein, the solid microparticles comprise two types of nanoparticles and microparticles; by way of example, the former include, but are not limited to, nano-silica, nano-alumina, nano-montmorillonite, nano-calcium carbonate, graphene, cellulose crystallites, nano-polymethylmethacrylate particles, nano-polystyrene particles, nano-iron oxide particles, nano-mica, nano-silicon nitride, and the like; the latter include, but are not limited to, submicron or micron sized silica particles, alumina particles, polymethylmethacrylate particles, polystyrene particles, starch particles, mica, silicon nitride, and the like. The shape of the solid microparticles can be spheres, ellipsoids, discs, other regular and irregular polyhedrons and the like, the surface of the solid microparticles can be smooth or rough, and spheres and ellipsoids are preferred; the surface of which is optionally also modified organically and/or inorganically.

Wherein, when the dispersion medium is selected from liquid, it includes but is not limited to organic matter, mineral oil, polymer matrix, etc., and specifically, as examples, the dispersion medium includes but is not limited to water, polyethylene glycol, polypropylene glycol, liquid paraffin, vegetable oil, mineral oil, silicone oil, ionic liquid, plasticizer, liquid metal, dilatant fluid (such as boron-containing dynamic polymer), and mixtures thereof, etc.; when the dispersion medium is selected from solids, it includes, but is not limited to, low Tg crosslinked polymers, gels, dilatant crosslinked polymers (e.g., boron containing crosslinked dynamic polymers and hybrid crosslinked dynamic polymers).

In the embodiment of the present invention, when the dispersion liquid contains inorganic solid microparticles and organic dispersion medium, the dispersion liquid may optionally contain a coupling agent and/or a surfactant, so that the solid microparticles can be more uniformly dispersed in the dispersion medium, for example, silane coupling agents such as KH550, KH560 and a1120, and coupling agents such as titanates, aluminates, organochromosomes, phosphates, zirconates and stannates.

In the present invention, it is particularly pointed out that the dispersible dilatant dispersion is not used as a dilatant polymer/dilatant dispersion layer by itself, but is swollen or dispersed in a polymer network, or is dispersed in other self-supporting polymer materials with pores and cavities by coating, dipping and the like to provide dilatancy. Such polymeric materials include, but are not limited to, polymeric foams, fabrics, and the like. By way of example, the polymer foam includes, but is not limited to, polyurethane foam, polyamide foam, polyvinyl chloride foam, polyethylene foam, polypropylene foam, ethylene-vinyl acetate copolymer foam, silicone foam, and the like. By way of example, the fiber fabric includes, but is not limited to, an ultra-high molecular weight polyethylene fiber fabric, a polypropylene fiber fabric, a polyurethane fiber fabric, an aramid fiber fabric, a polyester fiber fabric, a spandex fiber fabric, a carbon fiber fabric, other functional fiber fabrics, a mixed fiber fabric containing two or more fibers, and the like; the fiber fabric may be two-dimensional or three-dimensional, and is more preferred because the three-dimensional fiber fabric has higher porosity and can hold more dispersion. In the present invention, it is more preferable that the dispersible dilatant composition is directly dispersed in the polymer matrix and forms a phase-separated dispersed phase at the time of processing and molding.

In the invention, the solid microparticles and the dispersion liquid required for realizing the dispersibility dilatancy have rich commercial sources, and the dispersion process does not need to carry out complex chemical reaction, thereby having the characteristic of high performance controllability. The dispersion of inorganic particles is also characterized by puncture resistance.

In the embodiment of the invention, the aerodynamic dilatancy structure is formed by regulating the open-cell structure of the foam, and when the open-cell surface area ratio is reduced, the rebound time is increased, and the dilatancy is enhanced. In order to obtain suitable dilatancy, the ratio of open cell area to cell surface area is preferably from 3% to 20%, more preferably from 5% to 15%, more preferably from 5% to 10%.

In the present invention, the aerodynamic dilatant structure can be obtained at least by adding a suitable amount of a pore former/porogen. The cell opener/porogen acts to break the cell walls as the polymer reacts to form a foam, thereby promoting the formation of an open cell structure. The types and the adding contents of the pore-forming agent/pore-foaming agent are not particularly limited, and can be reasonably regulated and controlled according to actual needs to obtain the polymer foam with different open area ratios and adjustable dilatancy. By way of example, for polyurethane foams, the cell opener/porogen may be selected from, but is not limited to: ethylene oxide homopolymer polyol or random copolymer polyol of ethylene oxide and a small amount of propylene oxide with the molecular weight of more than 5000Da and the hydroxyl functionality of not less than 5, and propylene oxide homopolymer monohydric alcohol with the molecular weight of 1000-8500 Da and the hydroxyl functionality of 1. In the invention, the fiber can be subjected to three-dimensional forming to obtain a cell structure with open pores or semi-open pores; abundant pore structures can also be obtained by 3D printing.

According to the invention, the strength of the dilatancy can be controlled by virtue of a pneumatic cellular structure, and through the design of a special cellular structure, the composite material can obtain a certain dilatancy under energy impact, so that the energy absorption and protection performance of the composite material is improved. The aerodynamic dilatancy has the characteristic of low temperature sensitivity, so that relatively stable dilatancy performance can be kept in a wider temperature range, and the cell structure with local open pores can reduce the shrinkage rate of foam after cooling and improve the shape stability of the composite material.

The skinned polymeric foam particles, which may be chemically cross-linked (including conventional covalent cross-linking and/or dynamic covalent cross-linking), may also be physically cross-linked, preferably physically cross-linked and/or dynamic covalent cross-linking.

In the present invention, the expandable polymer matrix is divided according to the main chain skeleton structure, which includes but is not limited to carbon chain structure, carbon-hetero chain structure, element organic chain structure, and carbon-hetero element chain structure.

In the present invention, the carbon chain structure, the main chain of which is composed of carbon atoms, is selected from, but not limited to, any of the following groups, any of unsaturated forms, any of substituted forms, any of hybridized forms, and combinations thereof: polyolefin-based chains such as polyethylene chains, polypropylene chains, polyisobutylene chains, polystyrene chains, polyvinyl chloride chains, polyvinylidene chloride chains, polyvinyl fluoride chains, polytetrafluoroethylene chains, polytrifluorochloroethylene chains, polyvinyl acetate chains, polyvinyl alkyl ether chains, polybutadiene chains, polyisoprene chains, polychloroprene chains, polynorbornene chains, and the like; polyacrylic acid chains such as polyacrylic acid chains, polyacrylamide chains, polymethyl acrylate chains, polymethyl methacrylate chains, and the like; polyacrylonitrile-based chains such as polyacrylonitrile chains and the like; preferred are polyethylene chains, polypropylene chains, polystyrene chains, polyvinyl chloride chains, polybutadiene chains, polyisoprene chains, polyacrylic acid chains, polyacrylamide chains, and polyacrylonitrile chains.

In the present invention, the main chain of the carbon-hetero chain structure is composed of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, etc., and is selected from, but not limited to, any of the following groups, any of unsaturated forms, any of substituted forms, any of hybridized forms, and combinations thereof: it is selected from polyether chains such as polyethylene oxide chains, polypropylene oxide chains, polytetrahydrofuran chains, epoxy resin chains, phenolic resin chains, polyphenylene ether chains, and the like; polyester-based chains such as polycaprolactone chains, polypentalactone chains, polylactide chains, polyethylene terephthalate chains, unsaturated polyester chains, alkyd resin chains, polycarbonate chains, bio-polyester chains, liquid crystal polyester chains, and the like; polyamine chains such as polyamide chains, polyimide chains, polyurethane chains, polyurea chains, polythiourethane chains, urea resin chains, melamine resin chains, liquid crystal polymer chains, and the like; polysulfide chains such as polysulfone chains, polyphenylene sulfide chains, etc.; polyethylene oxide chains, polytetrahydrofuran chains, epoxy resin chains, polycaprolactone chains, polylactide chains, polyamide chains, polyurethane chains, polyurea chains are preferred.

In the present invention, the molecular main chain of the organic chain structure of the element is composed of heteroatoms of inorganic elements such as silicon, boron and phosphorus, and optionally heteroatoms such as nitrogen, oxygen and sulfur, and is selected from, but not limited to, any of the following groups, any of unsaturated forms, any of substituted forms, any of hybridized forms, and combinations thereof: silicone polymer chains such as a polyorganosiloxane chain, a polyorganosiloxane nitrogen chain, a polyorganosiloxane sulfur chain, a polyorganopolysiloxane chain; organoboron polymer chains such as organoborane chains, polyorganoborazine chains, polyorganoborasulfane chains, polyorganoboraphosphoalkane chains, and the like; an organophosphorus-based polymer chain; an organolead-based polymer chain; an organotin-based polymer chain; an organic arsenic-based polymer chain; an organic antimony-based polymer chain; polyorganosiloxane chains, polyorganoborane chains are preferred.

In the present invention, the carbon-heteroatom chain structure, whose molecular main chain is composed of carbon atoms and heteroatoms of inorganic elements such as silicon, boron, phosphorus, and the like, and optionally heteroatoms such as nitrogen, oxygen, sulfur, and the like, is selected from, but not limited to, any of the following groups, any of unsaturated forms, any of substituted forms, any of hybridized forms, and combinations thereof: a carboheteroaganosilane chain, a carboheteroaganosiloxane chain, a carboheteroaorganosilboran chain, a carboheteroaorganosilazane chain, a carboheteroaganosiloxathiolane chain, a carboheteroaorganoborane chain, a carboheteroaorganoborazoxane chain, a carboheteroaorganoborethiane chain, a carboheteroaorganophosphorophosphane chain; preference is given to carboheteroaganosiloxane chains, carboheteroaganosiloxanes chains, carboheteroaorganoborane chains.

In the embodiment of the present invention, the expandable polymer matrix is preferably a polymer widely used in the art for preparing foamed materials, and includes, but is not limited to, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polybutadiene, polyisoprene, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, polyacrylic acid, polyacrylamide, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polytetrahydrofuran, epoxy resin, phenol resin, polycaprolactone, polylactide, unsaturated polyester, urea-formaldehyde resin, polyvinyl formal resin, polycarbonate, polyamide, polyimide, polyurethane, polyurea, polyethylene terephthalate, polybenzimidazole, polyorganosiloxanes, more preferably polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, epoxy resin, phenol resin, unsaturated polyester, polyamide, polyurethane, urea formaldehyde resin, polyorganosiloxanes, more preferably ethylene-vinyl acetate copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, polyurethane, polyorganosiloxanes, most preferably polyurethane; the Shore hardness of the selected polyurethane is preferably 10A-95A, and more preferably 20A-80A.

Compared with other polymer matrixes, the polyurethane has the advantages of high wear resistance, high elasticity, fatigue resistance, chemical corrosion resistance and the like, and the composite material prepared by taking the polyurethane as the matrix can particularly show good rebound resilience and impact resistance, so that the polyurethane can be widely applied to manufacturing high-performance shoe materials and sports protection materials.

In the embodiment of the present invention, in principle, all commercially available polyurethanes are suitable as the raw material of the present invention, but the corresponding polyurethane resin may be selected according to the requirements of the actual foam material application and the applicable range of the processing equipment conditions. For example, polyurethane resins having a relatively low melting point (< 150 ℃) and containing relatively high soft segment components are preferred as raw materials for soft-foam polyurethane applications; while the polyurethane resin having a higher melting point (150 ℃ C. and 250 ℃ C.) and containing a higher hard segment component is preferred as a raw material for the hard bubble polyurethane.

In addition, the expandable polymer can also be the composition of various polymers and related fillers and auxiliary agents thereof.

In the embodiment of the present invention, the polyol compound includes, but is not limited to, small molecule polyol, oligomer and high molecule polyol.

In the embodiment of the present invention, as specific examples thereof, there may be mentioned small-molecule polyols including, but not limited to, Ethylene Glycol (EG), Propylene Glycol (PG), 1, 4-butanediol, diethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 6-hexanediol, octanediol, nonanediol, decanediol, diethylene glycol, Trimethylolpropane (TMP), glycerol, pentaerythritol, xylitol, sorbitol, and the like; it is possible to list oligomer and polymer polyols including, but not limited to, polyester polyols, polyether polyols, polyolefin polyols, polycarbonate polyols, polyorganosiloxane polyols, polysulfone polyols, vegetable oil polyols and other polymer polyols, etc., and also copolymers and modified forms thereof.

In the embodiment of the present invention, the polyamine compound includes, but is not limited to, small molecule polyamines, oligomers, and high molecule polyamines, including, but not limited to, aromatic polyamines, aliphatic polyamines, and the like, which are shown below.

In the embodiment of the present invention, specific examples of the small-molecule aromatic polyamine include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, m-phenylenediamine, tris (dimethylaminomethyl) phenol, diaminodiphenylmethane, 3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), 3, 5-dimethylthiotoluenediamine (DMTDA), 3, 5-diethyltoluenediamine (DETDA); specific examples of the small-molecular aliphatic polyamine include methylenediamine, 1, 2-ethylenediamine, propylenediamine, 1, 2-diaminopropane, 1, 3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylaminopropylamine, diethylenetriamine, N-aminoethylpiperazine, triethylenetetramine, N '-dimethylethylenediamine, N' -diethylethylenediamine, N '-diisopropylethylenediamine, N' -dimethyl-1, 3-propanediamine, N '-diethyl-1, 3-propanediamine, N' -diisopropyl-1, 3-propanediamine, N '-dimethyl-1, 6-hexanediamine, N' -dimethylethylenediamine, N-diaminohexane, N '-dimethylethylenediamine, N-aminoethylpropane, N-aminoethylpiperazine, triethylenetetramine, N' -dimethylethylene, N, N '-diethyl-1, 6-hexanediamine, N', N ″ -trimethylbis (hexamethylene) triamine, and the like.

As oligomers and polymeric polyamines include, but are not limited to, polyamines based on polyesters, polyethers, polyolefins, polycarbonates, polyorganosiloxanes, vegetable oils and other polymers, and the like. Specific examples thereof include copolyether diamine, amino-terminated polyether having an arylamino group at the terminal, and amino-terminated dimethylsilicone oil.

In embodiments of the present invention, the polythiol compound includes, but is not limited to, small molecule polythiol, oligomer, and polymer polythiol compounds.

In the embodiment of the present invention, as the small molecule polythiol compound, for example, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 2-butanedithiol, 1, 3-butanedithiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol, 1, 10-decanedithiol, 2, 3-butanedithiol, dimercaptoethyl sulfide, 3, 7-dithia-1, 9-nonanedithiol, 3-mercapto- β -4-dimethylcyclohexylethanethiol, 1, 4-benzenedithiol, o-benzenedithiol, 3, 4-methanedithiol, 1, 5-naphthalenedithiol, LUbutanedithiol, 4' -dimercaptodiphenyl sulfide, dimercapto-3, 6-dioxaoctane, 1, 5-mercapto-3-thiopentane, 1, 3, 5-triazine-2, 4, 6-trithiol, etc. as well as the small molecule polythiol compound, the polyvalent compound may include, an oligomeric or other polymer, a polyether, an oligomeric or a polyether based on a plant, a polyether, and the like.

In embodiments of the present invention, the isocyanate compounds include, but are not limited to, small molecule, oligomeric, and polymeric polyisocyanate compounds.

In embodiments of the present invention, the small molecule isocyanate includes, but is not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), polymethylene polyphenyl isocyanate (PAPI), liquefied MDI, dicyclohexylmethane diisocyanate (HMDI), Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), Xylylene Diisocyanate (XDI), dimethylbiphenyl diisocyanate (TODI), 1, 4-cyclohexane diisocyanate (CHDI), tetramethylm-xylylene diisocyanate (m-TMXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), cyclohexanedimethylene diisocyanate (HXDI), norbornane diisocyanate (NBDI), TDI dimer, toluene diisocyanate (TDI I), toluene diisocyanate (MDI), toluene diisocyanate (HDI), toluene diisocyanate (HDDI), toluene diisocyanate (NBDI), toluene diisocyanate (TDI dimer), toluene diisocyanate (MDI), toluene diisocyanate (, Triphenylmethane Triisocyanate (TTI), 4', 4 ″ -triphenyltriisocyanate thiophosphate (TPTI), HDI trimer, IPDI trimer, TDI trimer, MDI trimer, TDI-TMP adduct, etc., wherein the isocyanate is preferably Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI); oligomeric and polymeric isocyanate compounds include, but are not limited to, polyisocyanate compounds based on polyesters, polyethers, polyolefins, polycarbonates, polyorganosiloxanes, vegetable oils, and other polymers, and the like.

In the present invention, the intrinsic type dilatant polymer itself has dilatancy without being filled, dispersed or mixed with non-polymer components. It should be noted that, in the present invention, an intrinsic dilatant polymer matrix may also be a polymer, which may be a composite of an intrinsic dilatant polymer and an extrinsic dilatant polymer. Furthermore, when non-covalent forces are formed between the components of a polymer composition and dilatancy occurs through the non-covalent forces, the composition is also considered to be an intrinsically dilatant polymer.

The composite of the present invention, wherein the skinned polymeric foam particles (foam particle phase) and the dynamic polymer and optionally other polymeric components (collectively referred to as the polymer phase) are blended with each other, the foam particle phase and the polymer phase can form any suitable aggregate structure, including but not limited to: the foam particle phase is a discontinuous dispersed phase, and the polymer phase is a continuous phase matrix; the foam particle phase is a semi-continuous dispersed phase, a partially continuous structure above a percolation threshold is formed by mutual contact of the foam particles, and the polymer phase is a continuous phase matrix; the foam particle phase is a continuous dispersed phase, a complete continuous structure above a percolation threshold is formed by mutual contact of the foam particles, and the polymer phase is a continuous phase matrix; the foam particle phase and the polymer phase are discontinuous phases, wherein one layer of foam particle phase and one layer of polymer phase are alternated layer by layer and the foam particles are bonded by the dynamic polymer, and the two layers (the foam particle phase layer is separated in the middle) of dynamic polymer are not contacted; the foam particle phase and the polymer phase are discontinuous phases with each other, wherein the foam particles are bonded through the dynamic polymer in two or more directions, and the dynamic polymer at different positions is not contacted with each other; the foam particle phase and the polymer phase are continuous with each other, wherein the foam particles are bonded to each other in two or more directions by the dynamic polymer, but the foam particles form a continuous phase by contacting with each other, as does the dynamic polymer.

In a preferred embodiment of the invention, the dynamic polymer in the composite is the continuous phase and the polymeric foam particles are the discontinuous, dispersed phase. In this embodiment, the dynamic polymer serves as a continuous phase versus a dispersed phase of the skinned polymer foam particles to provide good protection and adhesion, and when the composite material is damaged, the dynamic polymer can exhibit self-healing properties, reusability, recyclability, and functional properties such as shape memory and super-toughness in the course of daily use. The distribution of the foam particle phase in the polymer continuous phase may be spherically dispersed, may be rod-shaped dispersed, may be lamellar dispersed, may be network dispersed, may be irregular such as strip or block dispersed, or may be a combination of the above-mentioned dispersed forms, depending on the foam particle shape and aggregation form thereof, and the foam particle phase may or may not have compatibility with the polymer phase, preferably compatibility, to promote interfacial adhesion and improve mechanical properties.

In a preferred embodiment of the invention, the polymer foam particles and the dynamic polymer in the composite material are in a continuous phase with each other and the polymer foam particles themselves form a matrix by fusion/bonding. In this embodiment, the dynamic polymer serves as a continuous phase to the polymer foam particles to provide bonding, it can show different dynamic characteristics and response capability under different environmental conditions of heating, illumination, pH, oxidation reduction and the like, the dynamic property of the composite material is rich and adjustable, the composite material is favorable for absorbing energy by utilizing the dynamic reversibility, thereby having synergistic buffering and energy absorption effects with the foam particles and being continuous polymer foam particles with skins, it has excellent elasticity and high rebound effect, can generate large-amplitude compression deformation under the action of external force, effectively disperse, absorb and dissipate external impact energy, is favorable for leading the composite material to have dynamic property and simultaneously obtain high rebound resilience, and the composite material can be recovered as soon as possible after impact or compression, and excellent rebound resilience and shock absorption and buffer characteristics are provided for the dynamic polymer serving as a continuous phase.

In the embodiment of the invention, the aggregation state structures of the polymer foam particles and the dynamic polymer in the composite material can be adjusted according to the actual needs of product performance.

In the present invention, the polymer phase, which may be non-crosslinked or crosslinked, is selected from the group consisting of chemical crosslinking selected from the group consisting of ordinary covalent crosslinking and dynamic covalent crosslinking, and physical crosslinking selected from the group consisting of supramolecular interaction crosslinking. The crosslinking can also be a hybrid of various crosslinks. In embodiments of the present invention, dynamic covalent crosslinking and/or supramolecular interaction crosslinking are preferably employed to facilitate self-healing and recyclability.

In the present invention, it is preferable that the polymer and the dynamic polymer in the skin-carrying polymer foam particles constituting the composite material are selected from polymer matrices having good compatibility, thereby enabling good compatibility and adhesion between the foam particle phase and the polymer phase, and preventing the composite material from being broken at the interface between the foam particle and the dynamic polymer when being subjected to an external force, thereby obtaining a composite material having good mechanical properties, such as tear propagation resistance and rebound resilience.

In a preferred embodiment of the present invention, the expandable polymer used for the preparation of the particles of the skinned polymer foam also contains at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain. That is, the skinned polymeric foam particles can be dynamic polymeric foam particles. Dynamic components are introduced into foam particles of the composite material, so that the foam particle phase has dynamic characteristics, and the polymer foam particles are prepared by selecting dynamic polymers as expandable polymers, so that the orthogonal and/or synergistic regulation of the dynamic characteristics of the composite material can be achieved by respectively regulating and controlling the dynamic characteristics of the foam particles and the dynamic polymers.

In a preferred embodiment of the invention, the expandable polymer used for the preparation of the particles of the skinned polymer foam also contains at least one force-sensitive group in its polymer chain and/or at least one force-responsive component blended in the polymer; under the action of mechanical force, the force sensitive groups and/or force response components in the foam particles and the expandable polymer are chemically and/or physically changed to realize force response. That is, the skinned polymer foam particles may be force-responsive polymer foam particles. By selecting the skinned polymer foam particles containing force sensitive groups and/or force response components, the composite material can not only obtain dynamic property, but also embody the force response characteristics such as force-induced discoloration, force-induced luminescence, force-induced fluorescence, force-induced crosslinking, force-induced conductivity, force-induced release of small molecules and the like under the action of mechanical force, and compared with the traditional material, the composite material has excellent and practical functionality, thereby expanding the application range of the composite material and being put into more frontier and more special fields for use.

In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo chemical and/or physical changes of structure under the action of mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly generating chemical and/or physical signal changes, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, free radical, catalysis, redox, addition, condensation, substitution, exchange, elimination, decomposition, Polymerization, cross-linking, coordination, hydrogen bonding, host-guest bonding, ionic bonding, change of pi-pi stacking signal/performance, ionic bonding, degradation, change of viscosity signal/performance, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response performance/effect.

In the present invention, the force-sensitive moiety includes covalent type and non-covalent type. Wherein, the covalent type force sensitive element is mainly related to chemical changes such as breaking, eliminating, bonding, isomerization and the like of covalent bonds under the action of mechanical force, and comprises but not limited to homolytic cleavage, heterolytic cleavage, reverse cyclization, electrocyclic ring opening, bending activation, elimination, addition, isomerization and the like; the non-covalent force sensitive element mainly relates to physical changes such as dissociation of a supramolecular complex, disassembly and assembly of an assembly body, separation of a composition, separation of an aggregate and the like under the action of mechanical force.

In the present invention, the force sensitive groups include single force sensitive groups and complex force sensitive groups. Wherein the single force-sensitive moiety comprises only one force-sensitive element or only one force-sensitive element in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-responsive signal, comprising both covalent single force-sensitive moieties and non-covalent single force-sensitive moieties. Wherein, the composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and includes but not limited to tying structures, gating structures, parallel structures, tandem structures, and two or more of tying, gating, parallel and tandem structures, and multi-composite structures formed by multi-stage combination of the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.

In the present invention, the division is made by a force-activated reaction mechanism, and the covalent single force sensitive groups include, but are not limited to, the following groups: covalent single-force sensitive groups based on homolytic mechanism, covalent single-force sensitive groups based on heterolytic mechanism, covalent single-force sensitive groups based on reverse cyclization mechanism, covalent single-force sensitive groups based on electrocyclization mechanism, covalent single-force sensitive groups based on flexural activation mechanism, and covalent single-force sensitive groups based on other mechanisms.

In the present invention, the division is performed in a complex manner, and the non-covalent single force sensitive groups include, but are not limited to, the following groups: non-covalent single force sensitive groups based on supramolecular complexes, non-covalent single force sensitive groups based on supramolecular assemblies, non-covalent single force sensitive groups based on compositions, non-covalent single force sensitive groups based on aggregates.

In the present invention, covalent single force sensitive groups based on the homolytic mechanism include, but are not limited to, the following series: peroxide series, disulfo/polysulfide series, diselenide/polyselenide series, azonitrile series, bisarylfuranone series, bisarylcyclic ketone series, bisarylcyclopentenedione series, bisarylchromene series, arylbiimidazole series, arylethane series, dicyanotetrarylethane series, arylpinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane-substituted ethane series, bifluorene series, allylsulfide series, thio/seleno ester series.

In the invention, the covalent single force-sensitive group of the peroxide series homolysis mechanism refers to a force-sensitive group containing a peroxide force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.

A typical structure of the formula 1-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent single force-sensitive group of the disulfide/polysulfide series homolytic mechanism refers to a force-sensitive group containing disulfide/polysulfide force-sensitive elements, and the structural formula thereof includes but is not limited to the following types:

wherein m is the number of sulfur atoms connected by a single bond, and the value of m is a certain specific integer value of more than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;

wherein the content of the first and second substances,

indicates that n is connected with

An aromatic ring of (2); wherein the value of n is 0, 1 or an integer greater than 1; the symbols are the sites connected with other structures in the formula, and if not specifically noted, the symbols appearing hereinafter have the same meaning and are not repeated; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions

Are of the same or different structureThe same is carried out; in order to increase the conjugation effect and the steric hindrance, promote the homolytic fracture of the force sensitive group under the action of the mechanical force, facilitate the stabilization of the formed free radical and obtain the reversible force-activated characteristic,

said

Further preferred is at least one of the following structures, but the present invention is not limited thereto:

wherein L is₁Are divalent linking groups, each independently selected from, but not limited to:

l in different positions₁Are the same or different; wherein L is₂Are divalent linking groups, each independently selected from, but not limited to: a direct bond,

L in different positions₂Are the same or different;

wherein R is¹、R²、R³、R⁴Each independently selected from any suitable atom (including hydrogen atoms), substituent; the substituent contains a hetero atom or does not contain a hetero atom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure is not particularly limited, including but not limited toThe cyclic structure is selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, and is preferably an aliphatic ring and an aromatic ring. In general terms, R¹、R²、R³、R⁴Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl, and combinations of two or more of the foregoing. In order to increase the steric hindrance of nitrogen atoms in the force-sensitive groups, promote the homolytic cleavage of the force-sensitive groups under the action of mechanical force, facilitate the stabilization of the formed free radicals, promote the coupling of the free radicals or the reversible exchange of the force-sensitive groups, and obtain good reversible performance, R¹、R²、R³、R⁴Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Heteroalkyl, cyclic structure C_1-20Alkyl, C of cyclic structure_1-20Heteroalkyl group, C_1-20Aryl radical, C_1-20A heteroaryl group; in general terms, the structures in the general formulae 1-B-5, 1-B-7

said

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one of the ring-forming atoms of the aliphatic ring is a nitrogen atom, the rest of the ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms, and hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; in order to increase the steric hindrance of the nitrogen atom in the force-sensitive group, promote homolytic cleavage of the force-sensitive group under the action of mechanical forces, facilitate stabilization of the free radicals formed, and promote coupling of said free radicals

said

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation. It is to be expressly noted that, when in a structure "

Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain which may or may not participate in force activation, "at least one of the left and right sides of the activatable bond in the structure or a force-sensitive group comprising the structure

With substituted or supramolecular polymer chains participating in force activation, the force being transmitted through these chains

Acting on the force sensitive groups, wherein the included angle formed by the acting forces on the left side and the right side is not higher than 180 degrees, and preferably smaller than 180 degrees; unless otherwise indicated, appear hereinafter "

Each independently linked to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation "have the same meaning and are not repeated.

Specifically, typical structures of the formulae 1-B-1 to 1-B-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the diselenide/polyselene series homolysis mechanism refers to a force sensitive group containing diselenide/polyselene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:

wherein m is the number of selenium atoms connected by a single bond, and the value of m is a certain specific integer value greater than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein R is¹、R²、R³、R⁴The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.

Specifically, typical structures of the formulae 1-C-1 to 1-C-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

independently of one another and participating in force-activated substitution polymerizationChains of matter or supramolecular polymers.

In the invention, the covalent single force sensitive group of the azonitrile series homolytic mechanism refers to a force sensitive group containing azonitrile force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from, but not limited to, a hydrogen atom, a halogen atom, a heteroatom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl groups, and combinations of two or more of the foregoing, preferably selected from hydrogen atoms, halogen atoms, C_1-20Alkyl radical, C_1-20Heteroalkyl group, more preferably selected from hydrogen atom, C_1-5Alkyl radical, C_1-5Heteroalkyl, more preferably selected from cyano, methyl, ethyl, propyl, butyl;

A typical structure of the formula 1-D-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the bisaryl furanone series homolytic mechanism refers to a force sensitive group containing bisaryl furanone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w₁Is a divalent linking group, each of which is independently selected from, but not limited to

Is preferably selected from

Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure

With or without looping.

Wherein the structure represented by formula 1-E-1 is preferably selected from at least a subset of the following general structures:

wherein each G is independently selected from

Said

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein, W, W₁、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1;

wherein the content of the first and second substances,

to be connected with n

An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group; at different positions in the same general formula

Are the same or different; by way of example, the

May be selected from at least one of the following structures, but the invention is not limited thereto:

said

wherein L is₁、L₂The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

A typical structure of the formula 1-E-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₁、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-E-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the biaryl cyclic ketone series homolysis mechanism refers to a force sensitive group containing biaryl cyclic ketone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w₂Is a divalent linking group, each of which is independently selected from, but not limited to

Is preferably selected from

With or without looping.

Wherein the structure represented by formula 1-F-1 is preferably selected from at least a subset of the following general structures:

wherein, W, W₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.

A typical structure of the formula 1-F-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W, W₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-F-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the diarylcyclopentenedione series homolytic mechanism refers to a force sensitive group containing diarylcyclopentenedione force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;

With or without looping.

Wherein the structure represented by formula 1-G-1 is preferably selected from at least a subset of the following general structures:

wherein, W,

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; definition, selection range, preferred range of GThe general formula is 1-E-1-1;

A typical structure of the formula 1-G-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W,

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the general formula 1-G-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the bisaryl chromene series homolytic mechanism refers to a force sensitive group containing bisaryl chromene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, W₃Is a divalent linking group, each of which is independently selected from, but not limited to

V, V' are each independently selected from carbon atoms, nitrogen atoms; when V, V 'is a nitrogen atom, V, V' is linked to

Is absent;

Cyclopentadiene rings or no rings.

Wherein the structure represented by formula 1-H-1 is preferably selected from at least a subset of the following general structures:

wherein, W₃、V、V’、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1;

Among them, the structure represented by the general formula 1-H-1 further preferably has a structure represented by the following formula:

wherein, W₃、V、V’、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

A typical structure of the formula 1-H-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₃、

The definition, selection range and preferred range of (1-H-1) are the same; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the formula 1-H-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the aryl biimidazole series homolytic mechanism refers to a force sensitive group containing aryl biimidazole force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

the two five-membered nitrogen heterocycles form a polycyclic structure formed by a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond through respective ring-forming atoms; according to different

The linkage, formula 1-I-1 includes but is not limited to one or more of the following isomers:

it should be noted that under the condition of the synthesis, the various isomers can be mutually converted, so that the six isomer motifs are regarded as the same structural motif in the invention;

Cyclopentadiene rings or no rings.

Wherein the structure represented by the general formula 1-I-1 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;

The typical structure of the formula 1-I-1 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; l is₁The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.

Specifically, the typical structure of the general formula 1-I-1 can be further exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the aryl ethane series homolysis mechanism refers to a force sensitive group containing aryl ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein R is₂Each independently selected from any suitable atom (including a hydrogen atom), substituent selected from hydroxy, phenyl, phenoxy, C, and substituted polymer chain with or without participation in force activation_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,

A typical structure of the formula 1-J-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₂The definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1;

In the invention, the covalent single force sensitive group of the dicyano tetraarylethane series homolysis mechanism refers to a force sensitive group containing dicyano tetraarylethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula 1-K-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the aryl pinacol series homolysis mechanism refers to a force sensitive group containing an aryl pinacol force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, W₄Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,

Preferably from a direct bond,

A typical structure of the formula 1-L-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₄The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1;

In the present invention, the covalent single force-sensitive group of the chain transfer series homolytic mechanism refers to a force-sensitive group containing a chain transfer force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:

wherein R is₂And

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; w₄The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1; r¹、R²、R³、R⁴The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5;

wherein R is₁Each independently selected from atoms (including hydrogen atoms), substituents, R at different positions₁Are the same or different in structure; wherein said substituents contain hetero atoms orA hetero atom is not contained, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R₁Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. In order to promote the homolytic fracture of the force sensitive group under the action of mechanical force, increase the oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate the coupling of the further free radical or participate in other free radical reactions, and obtain the reversible force-induced activation characteristic, the self-repairing performance and the self-enhancing performance, R₁Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene_1-20Hydrocarbyl/heterohydrocarbyl; r₁Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;

wherein, V₃Selected from selenium atom, tellurium atom, antimony atom, bismuth atom; wherein k is and V₃Connected to each other

The number of (2); when V is₃In the case of selenium or tellurium, k is 1 and represents only one

And V₃Connecting; when V is₃When it is an antimony atom or a bismuth atom, k is 2, which means that there are two

And V₃Are connected with two

Are the same or different in structure;

wherein, L 'is a divalent linking group, and the structures of L' at different positions are the same or different; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, each of said L' is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. In order to promote homolytic cleavage of the force sensitive group under the action of mechanical force, increase oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate further coupling of the free radical or participate in other free radical reactions, and obtain reversible force-induced activation property, self-repairing property and self-enhancing property, L' is respectively and independently preferably selected from acyl, acyloxy, acylthio, acylamino, oxyacyl, sulfuryl, phenylene and divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C_1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C_1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group₁To the carbon atom(s) of (a);

in general terms, the use of a single,in the general formulae 1-M-1 to 1-M-8

Preferably, the present invention is not limited to one selected from the following structures:

wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein R represents the number of R connected with a benzene ring, and the value of R is an integer selected from 0 to 5; wherein m is the number of repeating units, which can be a fixed value or an average value;

said

wherein, the definitions, selection ranges and preferred ranges of R, R and m are as described in the primary structure;

wherein the content of the first and second substances,

A typical structure of the formula 1-M-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein R is₂The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-1;

Typical structures of the general formula 1-M-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-2;

Typical structures of the general formulae 1 to M-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein, W₄The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-3;

Typical structures of the general formulae 1 to M-4 may be exemplified as follows, but the present invention is not limited thereto:

wherein m is defined, selected and preferredGeneral formula 1-M-4;

Typical structures of the general formulae 1 to M-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-5;

Typical structures of the general formulae 1 to M-6 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-6;

Typical structures of the general formulae 1 to M-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-7;

Typical structures of the formulae 1 to M-8 may be illustrated below, but the present invention is not limited thereto:

wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-8;

In the invention, the covalent single force sensitive group of the cyclohexadienone series homolytic mechanism refers to a force sensitive group containing cyclohexadienone force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4;

Typical structures of the formulae 1-N-1 to 1-N-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the tetracyanoethane series homolysis mechanism refers to a force sensitive group containing tetracyanoethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

Wherein the structure represented by formula 1-O-1 is preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3;

A typical structure of formula 1-O-1 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent single force-sensitive group of the cyanoacyl ethane series homolysis mechanism refers to a force-sensitive group containing cyanoacyl ethane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:

wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein, W₅Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,

Is preferably selected from

More preferably from

With or without looping.

Wherein the structure represented by formula 1-P-1 is preferably selected from at least a subset of the following general structures:

wherein, W, W₅、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-P-1.

A typical structure of the formula 1-P-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the adamantane substituted ethane series homolytic mechanism refers to a force sensitive group containing adamantane substituted ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein Ad is selected from the group consisting of bivalent or multivalent adamantyl and dimeric or multimeric derivatives thereof; by way of example, the Ad is selected from, but not limited to:

wherein the content of the first and second substances,

A typical structure of the formula 1-Q-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the bifluorene series homolysis mechanism refers to a force sensitive group containing bifluorene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein R is₃Each independently selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10An alkylaminoacyl group, a phenyl group, a substituted phenyl group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, wherein the substituent atom or the substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbon group substituent group, and a heteroatom-containing substituent group; wherein the content of the first and second substances,

Typical structures of the general formula 1-R-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force-sensitive group of the homolytic mechanism of the allyl sulfide series refers to a force-sensitive group containing allyl sulfide force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:

wherein, C¹、C²、C³Represents carbon atoms, and the numbers at the upper right corner of the carbon atoms are used for distinguishing carbon atoms at different positions so as to facilitate the accuracy and the conciseness of description;

wherein R is₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently selected from atoms (including hydrogen atoms), substituents; r₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently preferably selected from a hydrogen atom, a halogen atom, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20A hydrocarbon group/heterohydrocarbon group, the substituent atom or substituent group being not particularly limited; r₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently more preferably from a hydrogen atom, a halogen atom, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heterohydrocarbyl radical, C_1-20Hydrocarbyloxyacyl group, C_1-20Hydrocarbyl thioacyl, C_1-20Hydrocarbyl aminoacyl groups and substituents formed from combinations of two or more of the above groups; r₁ ¹、R₁ ²、R₁ ³、R₁ ⁴Each independently of the others is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl;

wherein Z is₂Is a divalent linking atom or a divalent linking group; when Z is₂When selected from divalent linking atoms, it is selected from S atoms; when Z is₂When the divalent linking group is selected, the divalent linking group contains a hetero atom or does not contain a hetero atom, and the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10; the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure or a cyclic structure; the cyclic structure is selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof, preferably an aliphatic ring and an aromatic ring(ii) a In general terms, Z₂Selected from, but not limited to, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed by a hydrocarbyl/heterohydrocarbyl group and a combination of two or more of the above groups, wherein the substituent atom or substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent group, and a heteroatom-containing substituent group; z₂More preferably divalent acrylic or methacrylic acid and its corresponding esters, divalent acrylamides or methacrylamides, N-mers of divalent styrene or methylstyrene (N.gtoreq.2) such as trimers, tetramers;

when Z is₂Selected from divalent linking atoms, Z₁Is and C²A divalent linking group in which the atoms are directly linked; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₁More preferably from divalent C_1-20Alkyl, divalent C_1-20Aromatic hydrocarbon radical, divalent C_1-20Alkoxy, divalent C_1-20Aryloxy, divalent C_1-20Alkylthio, divalent C_1-20Arylthio, most preferably selected from divalent C_1-20An alkylthio group; in particular, Z₁Preferably from methylene, methylene sulfide, ethylene, propylene, butylene, pentylene, hexylene, divalent phenyl ether, divalent benzyl, divalent ethoxy, divalent butoxy, divalent hexyloxy, most preferably selected from methylene sulfide; when Z is₂Selected from said divalent linking groups, Z₁Is and C²A divalent linking group in which the atoms are directly linked; the divalent linking group containing or not containing a hetero atomThe number of carbon atoms is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₁More preferably from divalent connecting group with electron-withdrawing effect, divalent connecting group substituted by electron-withdrawing effect substituent, so as to facilitate the homolytic cleavage of the force sensitive group and obtain more remarkable force-induced response effect; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group_1-20Hydrocarbyl/heterohydrocarbyl; by way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, an amide group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, a pyridylidene group;

wherein the content of the first and second substances,

A typical structure of the formula 1-S-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein n isThe number of the repeating units can be a fixed value or an average value, and n is an integer greater than or equal to 1;

In the invention, the covalent single force sensitive group of the thio/seleno ester series homolytic mechanism refers to a force sensitive group containing thio/seleno ester force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, W₆Each independently selected from a sulfur atom or a selenium atom;

wherein Z is₃A divalent linking group containing or not containing a heteroatom, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; by way of example, Z₃Selected from, but not limited to, divalent heteroatom linkers, divalent heteroatom group linkers, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein Z is₄Is a divalent linking group, the divalent linking group contains or does not contain heteroatoms, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1-20, more preferably 1-10, the structure is not particularly limited, and the divalent linking group comprises linear structure, branched structure or cyclic structure, the cyclic structure is selected from fatAromatic rings, ether rings, condensed rings, and combinations thereof, preferably aromatic rings; the divalent linking group is selected from but not limited to divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₄More preferably C substituted by cyano, alkyl, aryl, ester, amide, urea, carbamate_1-20Hydrocarbyl/heterohydrocarbyl;

wherein the content of the first and second substances,

Wherein the structure represented by formula 1-T-1 is preferably selected from at least a subset of the following general structures:

wherein, W₆、Z₄、

The definition, selection range and preferable range of (A) are the same as those of the general formula 1-T-1;

wherein Z is₅Selected from oxygen atom, sulfur atom, selenium atom, silicon atom, carbon atom, nitrogen atom; when Z is₅When it is an oxygen atom, a sulfur atom, or a selenium atom, R₁ ⁵、R₁ ⁶、R₁ ⁷Is absent; when Z is₅When it is a nitrogen atom, R₁ ⁵Exist, R₁ ⁶、R₁ ⁷Is absent; when Z is₅When it is a silicon atom or a carbon atom, R₁ ⁵、R₁ ⁶Exist, R₁ ⁷Is absent;

wherein R is₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently selected from an atom (including a hydrogen atom), a substituent; r₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently preferably selected from a hydrogen atom, a halogen atom, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl; r₁ ⁵、R₁ ⁶、R₁ ⁷、R₁ ⁸Each independently more preferably from a hydrogen atom, a halogen atom, C_1-20Alkyl radical, C_1-20Alkenyl radical, C_1-20Aryl radical, C_1-20Alkoxyacyl group, C_1-20Alkoxythioacyl, C_1-20Aryloxy acyl group, C_1-20Aryloxythioacyl, C_1-20Alkylthio acyl radical, C_1-20An arylthioacyl group;

wherein Z is₆Is a divalent linking group; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring. The divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z₆The divalent connecting group is preferably selected from a divalent connecting group with an electron-withdrawing effect and a divalent connecting group substituted by an electron-withdrawing effect substituent, so that the force sensitive group is split evenly and more remarkable force-induced response effect is obtained; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group_1-20Hydrocarbyl/heterohydrocarbyl. By way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited toNot limited to acyl, acyloxy, acylthio, amide, phenylene, nitro, sulfonic acid, aromatic hydrocarbon, cyano, halogen, trifluoromethyl-substituted phenylene, benzylidene, naphthylidene, pyrrolylidene, pyridylidene groups.

A typical structure of the formula 1-T-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the benzoyl series homolysis mechanism refers to a force sensitive group containing benzoyl force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein each Z is independently selected from carbon atom, silicon atom, germanium atom and tin atom, preferably selected from carbon atom, germanium atom and tin atom; each W is independently selected from an oxygen atom or a sulfur atom, preferably from an oxygen atom; wherein the content of the first and second substances,

Typical structures of the general formulae 1-S-1, 1-S-2, 1-S-3 may be exemplified as follows, but the present invention is not limited thereto:

in the present invention, covalent single force sensitive groups based on heterolytic mechanisms include, but are not limited to, the following series: triaryl sulfur salt series, o-phthalaldehyde series, sulfonic acid series, seleno/seleno-sulfur/seleno-nitrogen series, and mercapto-Michael addition bond series.

In the invention, the covalent single force sensitive group of the triaryl sulfate series heterolysis mechanism refers to a force sensitive group containing triaryl sulfate force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, wherein any two of the same ring structure

With or without looping.

A typical structure of the formula 2-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the ortho-phthalaldehyde series heterolysis mechanism refers to a force sensitive group containing ortho-phthalaldehyde force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:

wherein, the ring of M is aliphatic ring, ether ring or the combination of the aliphatic ring, the ether ring and the aromatic ring, the ring-forming atoms of the ring structure are respectively and independently carbon atoms, nitrogen atoms or other hetero atoms, and at least one ring-forming atom is oxygen atom; the hydrogen atoms attached to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

A typical structure of the formula 2-B-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force-sensitive group of the sulfonic acid group series heterolysis mechanism refers to a force-sensitive group containing a sulfonic acid group force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula 2-C-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force-sensitive group of the seleno-oxo/seleno-thio/seleno-nitrogen series heterofission mechanism refers to a force-sensitive group containing seleno-oxo/seleno-thio/seleno-nitrogen force-sensitive elements, and the structural general formula includes but is not limited to the following types:

wherein each W is independently selected from an oxygen atom, a sulfur atom; wherein the content of the first and second substances,

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, to the same atom

With or without looping.

Wherein the structures represented by the general formulae 2-D-1 and 2-D-2 are preferably selected from at least a subset of the following general structures:

wherein W is as defined for formula 2-D-1; wherein the content of the first and second substances,

indicates that n is connected with

A nitrogen-containing aromatic ring of (a); the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 5 to 8; except that at least one of the ring-forming atoms is a nitrogen atom and the ring and the selenium atom are connected through the nitrogen atom, the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the value of n is 0, 1 or an integer greater than 1; at different positions

Are the same or different; said

The structure of (a) is preferably selected from pyridine rings and substituted forms thereof;

any two of which are each independently attached to the same atom, including a hydrogen atom, a substituent, and a substituted polymer chain, with or without participation in force activation

With or without rings, any two of the same ring structure

With or without looping.

Typical structures of the general formulae 2-D-1, 2-D-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein X is selected from but not limited to fluorine atom, chlorine atom, bromine atom, cyano group, and isothiocyanato group, preferably from chlorine atom and bromine atom;

In the present invention, the covalent single force-sensitive group of the mercapto-michael addition bond series heterolysis mechanism refers to a force-sensitive group containing a mercapto-michael addition bond force-sensitive element, and the structural formula thereof includes but is not limited to the following types:

wherein X is selected from carbon group, ester group, amide group, thiocarbonyl group, thioester group, thioamide group, sulfone group, sulfonate group and phosphate group; y is an electron-withdrawing effect group including, but not limited to, aldehyde group, carbon group, ester group, carboxyl group, amide group, cyano group, nitro group, trifluoromethyl group, phosphoric acid group, sulfonic acid group, halogen atom;

With or without rings, on different carbon atoms

The electricity being able to link to form a ring, the carbon atom being attached to X

Or may be linked to form a ring, including but not limited to an aliphatic ring,Aromatic rings, ether rings, condensed rings, and combinations thereof.

Typical structures of the general formulae 2-E-1, 2-E-2, 2-E-3, 2-E-4 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, covalent single force sensitive groups based on the reverse cyclization mechanism include, but are not limited to, the following series: cyclobutane series, monoepoxybutane series, dioxetane series, dinitrocyclobutane series, cyclobutene series, triazole ring series, DA series, hetero DA series, light-controlled DA series, and [4+4] cycloaddition series.

In the invention, the covalent single force sensitive group of the cyclobutane series reverse cyclization mechanism refers to a single force sensitive group containing cyclobutane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, Q is independently selected from oxygen atom and carbon atom, and Q at different positions can be the same or different; b represents the number of connections to Q, respectively; when each Q is independently selected from oxygen atoms, b ═ 0; when each Q is independently selected from carbon atoms, b ═ 2;

Can be linked to form a ring, on different atoms

among them, the force sensitive group of the formula 3-A-1 is preferably selected from at least a subset of the following general structures:

wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different;

ar is independently selected from aryl, preferably phenyl, and Ar at different positions can be the same or different; n represents the number of connections to Ar; x₀Each independently selected from a halogen atom, preferably from a fluorine atom, a chlorine atom, a bromine atom;

Can be linked to form a ring, on different atoms

among them, the force sensitive group of the general formula 3-A-1-1 is preferably selected from the following general structure:

wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j 'is independently selected from oxygen atom and sulfur atom, and J' at different positions can be the same or different;

a typical structure of the formula 3-A-1-1 can be exemplified as follows:

wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j 'is independently selected from oxygen atom and sulfur atom, and J' at different positions can be the same or different; r, R₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-2 is preferably selected from the following general structure:

a typical structure of the formula 3-A-1-2 can be exemplified as follows:

wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j' is selected from oxygen atom and sulfur atom; r, R₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;

among them, the force sensitive group of the general formula 3-A-1-3 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-3 can be exemplified as follows:

wherein R is₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-4 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-4 can be exemplified as follows:

among them, the force sensitive group of the general formula 3-A-1-5 is preferably selected from the following general structure:

wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof;

typical structures of the general formula 3-A-1-5 can be exemplified as follows:

wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-6 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-6 can be exemplified as follows:

wherein, R, R₁、R₂、R₃Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-7 is preferably selected from the following general structure:

wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof; j' is selected from oxygen atom and sulfur atom;

typical structures of the general formula 3-A-1-7 can be exemplified as follows:

wherein, R, R₁、R₂、R₃、R₄Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-8 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-8 can be exemplified as follows:

wherein, R, R₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-A-1-9 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-9 can be exemplified as follows:

typical structures of the general formula 3-A-1-10 can be exemplified as follows:

typical structures of the general formula 3-A-1-11 can be exemplified as follows:

among them, the force sensitive group of the general formula 3-A-1-12 is preferably selected from the following general structure:

typical structures of the general formula 3-A-1-12 can be exemplified as follows:

in addition, the typical structure of the covalent single force sensitive group of the cyclobutane series reverse cyclization mechanism can also be exemplified as follows:

wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different; j' is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof;

a typical structure of the formula 3-A-2 can be exemplified as follows:

typical structures of the general formula 3-A-3 can be exemplified as follows:

typical structures of the general formula 3-A-4 can be exemplified as follows:

in the present invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the mono-heterocyclic butane series refers to a single force-sensitive group containing a mono-heterocyclic butane force-sensitive element, and the structural general formula thereof includes but is not limited to the following types:

wherein Q is selected from oxygen atom and carbon atom; b represents the number of connections to Q; when Q is selected from oxygen atom, b ═ 0; when Q is selected from carbon atoms, b ═ 2; d is selected from oxygen atom, sulfur atom, selenium atom, nitrogen atom and silicon atom; a represents the number of connections to D; when D is selected from oxygen atom, sulfur atom and selenium atom, a is 0; when D is selected from a nitrogen atom, a ═ 1; when D is selected from a silicon atom, a ═ 2;

Can be linked to form a ring, on different atoms

a typical structure of the formula 3-B-1 can be exemplified as follows:

among them, the force sensitive group of the general formula 3-B-2 is preferably selected from at least a subset of the following general structures:

in the present invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the dioxetane series refers to a single force-sensitive group containing dioxetane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:

wherein J is selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, a methylene group and substituted forms thereof; wherein Ar is selected from aromatic rings selected from monocyclic structures, polycyclic structures and condensed ring structures; the number of ring-forming atoms of the ring is not particularly limited, and a five-membered ring or a six-membered ring is preferable; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, and silicon atoms, and the hydrogen atoms attached to the ring-forming atoms may be substituted with any suitable substituent atom, substituent, or may be unsubstituted; wherein, the substituent atom or substituent group is not particularly limited and is selected from but not limited to heteroatom group, small molecule hydrocarbyl group, polymer chain residue; the substituent atoms or substituents are preferably selected from: halogen atom, cyano group, nitro group, trifluoromethyl group, C_1-20Alkyl radical, C_1-20Alkylsiloxy group, C_1-20Acyloxy, C_1-20Alkoxyacyl group, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20An alkylamino group. By way of example, suitable Ar may be selected from the following structures:

wherein, the symbol is the site connecting with other structures in the formula, if not specifically noted, the following symbol is the same meaning, and the description is not repeated; l is₁Is a divalent linking group selected from, but not limited to, oxygen atoms, sulfur atoms, secondary amine groups and substituted forms thereof, methylene groups and substituted forms thereof; l is₂Is a divalent linking group selected from, but not limited to, a direct bond, an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, a methylene group and substituted forms thereof, a carbonyl group, a thiocarbonyl group;

typical structures of covalent single force sensitive groups of the reverse cyclization mechanism of the dioxetane series can be exemplified as follows:

in the invention, the covalent single force sensitive group of the reverse cyclization mechanism of the diazocyclobutane series refers to a single force sensitive group containing a diazobutane force sensitive element, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:

a typical structure of the formula 3-D-1 can be exemplified as follows:

a typical structure of the general formula 3-D-2 can be exemplified as follows:

a typical structure of the general formula 3-D-3 can be exemplified as follows:

in the invention, the covalent single force sensitive group of the cyclobutene series reverse cyclization mechanism refers to a single force sensitive group containing cyclobutene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 membered ring, more preferably 6-12 membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above ring structures; n represents the number of linkages to the ring-forming atoms of the cyclic structure; each R is independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;

a typical structure of the formula 3-E-1 can be exemplified as follows:

wherein, R, R₁、R₂Each independently selected from any one of the following structures: hydrogen atom, hetero atom group, smallMolecular hydrocarbyl, polymer chain residue;

a typical structure of the general formula 3-E-2 can be exemplified as follows:

typical structures of the general formula 3-E-3 can be exemplified as follows:

typical structures of the general formula 3-E-4 can be exemplified as follows:

wherein, R, R₁Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

in the invention, the covalent single-force sensitive groups of the cyclobutane series, the monoheterocyclic butane series, the dioxetane series, the dinitrocyclobutane series and the cyclobutene series reverse cyclization mechanism can also be activated by other actions except mechanical force, for example, the covalent single-force sensitive groups of the cyclobutane series can be subjected to reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force sensitive groups; the dioxetane series covalent single force sensitive group can be subjected to reverse cyclization reaction under one or more of the activation effects of chemistry, biology, heat and the like so as to dissociate the force sensitive group.

In the invention, the covalent single force sensitive group of the triazole ring series reverse cyclization mechanism is a single force sensitive group containing a triazole ring force sensitive element, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:

wherein the content of the first and second substances,

among them, the force sensitive group of the formula 3-F-1 is preferably selected from at least a subset of the following general structures:

in the invention, the covalent single force sensitive group of the DA series reverse cyclization mechanism refers to a single force sensitive group containing DA force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following classes:

wherein I is selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;

Can be linked to form a ring, on different atoms

among them, the force sensitive group of the formula 3-G-1 is preferably selected from at least a subset of the following general structures:

wherein each R is independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;

a typical structure of the formula 3-G-1-1 can be exemplified as follows:

a typical structure of the formula 3-G-1-2 can be exemplified as follows:

typical structures of the general formula 3-G-1-3 can be exemplified as follows:

typical structures of the general formula 3-G-1-4 can be exemplified as follows:

a typical structure of the formula 3-G-2 can be exemplified as follows:

among them, the force sensitive groups of formula 3-G-3 are preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-G-3-1 can be exemplified as follows:

a typical structure of the general formula 3-G-3-2 can be exemplified as follows:

typical structures of the general formula 3-G-3-3 can be exemplified as follows:

typical structures of the general formula 3-G-3-4 can be exemplified as follows:

typical structures of the general formula 3-G-3-5 can be exemplified as follows:

typical structures of the general formula 3-G-3-6 can be exemplified as follows:

typical structures of the general formula 3-G-3-7 can be exemplified as follows:

typical structures of the general formula 3-G-3-13 can be exemplified as follows:

typical structures of the general formula 3-G-3-14 can be exemplified as follows:

typical structures of the general formula 3-G-3-19 can be exemplified as follows:

among them, the force sensitive groups of formula 3-G-4 are preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-G-4-1 can be exemplified as follows:

a typical structure of the general formula 3-G-4-2 can be exemplified as follows:

typical structures of the general formula 3-G-4-3 can be exemplified as follows:

typical structures of the general formula 3-G-4-4 can be exemplified as follows:

among them, the force sensitive groups of formula 3-G-5 are preferably selected from at least a subset of the following general structures:

among them, the force sensitive group of the general formula 3-G-5-1 is preferably selected from the following general structure:

a typical structure of the general formula 3-G-5-1-1 can be exemplified as follows:

a typical structure of the general formula 3-G-5-1-2 can be exemplified as follows:

wherein the content of the first and second substances,R、R₁each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive group of the general formula 3-G-5-2 is preferably selected from the following general structure:

among them, the force sensitive group of the general formula 3-G-5-3 is preferably selected from the following general structure:

among them, the force sensitive groups of formula 3-G-6 are preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-G-6-1 can be exemplified as follows:

among them, the force sensitive groups of formula 3-G-7 are preferably selected from at least a subset of the following general structures:

among them, the force sensitive group of the general formula 3-G-7-1 is preferably selected from the following general structure:

among them, the force sensitive group of the general formula 3-G-7-2 is preferably selected from the following general structure:

among them, the force sensitive groups of formula 3-G-8 are preferably selected from at least a subset of the following general structures:

in the invention, the covalent single force sensitive group of the hetero DA series reverse cyclization mechanism refers to a single force sensitive group containing a hetero DA force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein, P₁Selected from oxygen atom, sulfur atom, nitrogen atom, silicon atom, selenium atom; p₂Selected from carbon atoms, nitrogen atoms, silicon atoms; c. C₁、c₂Respectively represent and P₁、P₂The number of connected connections; when P is present₁Selected from oxygenWhen atom, sulfur atom, selenium atom, c₁0; when P is present₁、P₂When selected from nitrogen atoms, c₁、c₂1 is ═ 1; when P is present₁、P₂When selected from carbon atoms, silicon atoms, c₂2; i is selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;

Can be linked to form a ring, on different atoms

among them, the force sensitive group of the general formula 3-H-1 is preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-H-1-1 can be exemplified as follows:

a typical structure of the formula 3-H-1-2 can be exemplified as follows:

typical structures of the general formula 3-H-1-3 can be exemplified as follows:

typical structures of the general formula 3-H-1-4 can be exemplified as follows:

typical structures of the general formula 3-H-1-5 can be exemplified as follows:

among them, the force sensitive group of the general formula 3-H-2 is preferably selected from at least a subset of the following general structures:

among them, the force sensitive group of the general formula 3-H-3 is preferably selected from at least a subset of the following general structures:

among them, the force sensitive groups of the general formula 3-H-4 are preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-H-4-1 can be exemplified as follows:

a typical structure of the formula 3-H-4-2 can be exemplified as follows:

typical structures of the general formula 3-H-4-3 can be exemplified as follows:

typical structures of the general formula 3-H-4-7 can be exemplified as follows:

typical structures of the general formula 3-H-4-8 can be exemplified as follows:

typical structures of the general formula 3-H-4-9 can be exemplified as follows:

typical structures of the general formula 3-H-4-10 can be exemplified as follows:

typical structures of the general formula 3-H-4-13 can be exemplified as follows:

typical structures of the general formula 3-H-4-14 can be exemplified as follows:

typical structures of the general formula 3-H-4-15 can be exemplified as follows:

typical structures of the general formula 3-H-4-16 can be exemplified as follows:

typical structures of the general formula 3-H-4-19 can be exemplified as follows:

typical structures of the general formula 3-H-4-20 can be exemplified as follows:

typical structures of the general formula 3-H-4-21 can be exemplified as follows:

typical structures of the general formula 3-H-4-22 can be exemplified as follows:

among them, the force sensitive groups of the general formula 3-H-5 are preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-H-5-1 can be exemplified as follows:

a typical structure of the formula 3-H-5-2 can be exemplified as follows:

typical structures of the general formula 3-H-5-3 can be exemplified as follows:

typical structures of the general formula 3-H-5-4 can be exemplified as follows:

typical structures of the general formula 3-H-5-5 can be exemplified as follows:

wherein R is₁Selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive groups of the general formula 3-H-6 are preferably selected from at least a subset of the following general structures:

in the invention, the covalent single force sensitive group of the light-controlled DA series reverse cyclization mechanism refers to a single force sensitive group containing a light-controlled locking element and a DA element sensitive to mechanical force, wherein the DA element can be used as a part of the light-controlled locking element; the existence of the light-operated locking element enables the force-sensitive clusters to have different structures under different illumination conditions and show different response effects on mechanical force, thereby achieving the purpose of locking/unlocking the force-sensitive elements; under the condition of light-operated unlocking, the DA force-sensitive element can perform inverse DA chemical reaction under the action of mechanical force, so that the polymer directly and/or indirectly generates chemical signal change, specific response to mechanical force is achieved, and force-induced response performance/effect is obtained; when the force-sensitive element is locked, it cannot be activated by mechanical force to express the force-sensitive property, or is more difficult to be activated by mechanical force to express the force-sensitive property. By utilizing the characteristics, the mechanochemical performance of the material can be regulated and controlled by selecting specific illumination conditions, the locking/unlocking regulation effect is achieved, and the applicability and the functional responsiveness of the force sensitive group are improved. Wherein, ultraviolet light (generally, ultraviolet light with a wavelength range of 310-380 nm) is selected to lock the force sensitive groups, and visible light (generally, visible light with a wavelength range of more than 420 nm) is selected to unlock the force sensitive groups. The ultraviolet light and the visible light used as the light source in the present invention have various and unlimited sources, and may be ultraviolet light or visible light directly generated by a high pressure mercury lamp, a metal halogen lamp, a mercury lamp, a xenon lamp, an LED lamp, etc. with a desired wavelength, or ultraviolet light or visible light obtained by energy transfer (including up-conversion fluorescence or down-conversion fluorescence) of a fluorophore; the fluorophore may be selected from organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, organic-inorganic hybrid fluorophores, and the like.

wherein the content of the first and second substances,

represents a linkage to a polymer chain, a cross-linked network chain, a force-sensitive group, or any other suitable group/atom; difference on the same atom

Can be linked to form a ring, on different atoms

In the invention, the Diels-Alder force-sensitive element contains at least one of the following structural units:

wherein, K₀Selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom; a is₀Represents a group K₀The number of connected connections; when K is₀When selected from oxygen atom, sulfur atom, a₀0; when K is₀When selected from nitrogen atoms, a₀1 is ═ 1; when K is₀When selected from carbon atoms, a₀＝2。

In the invention, the covalent single force sensitive group of the reverse cyclization mechanism of the light-operated DA series has a structural general formula including but not limited to the following classes:

wherein, K₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₃、K₄Or K₅、K₆At least one of them is selected from carbon atoms; a is₁、a₂、a₃、a₄、a₅、a₆Respectively represent and K₁、K₂、K₃、K₄、K₅、K₆The number of connected connections; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from an oxygen atom and a sulfur atom₁、a₂、a₃、a₄、a₅、a₆0; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from nitrogen atoms, a₁、a₂、a₃、a₄、a₅、a₆1 is ═ 1; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atoms, a₁、a₂、a₃、a₄、a₅、a₆＝2；I₁、I₂、I₃Each independently absent or each independently selected from the group consisting of an oxygen atom, a1, 1 '-carbonyl group, a methylene group and substituted forms thereof, a1, 2-ethylene group and substituted forms thereof, a1, 1' -vinyl group and substituted forms thereof; when I is₁、I₂、I₃Each independently absent, b ═ 2; when I is₁、I₂、I₃Each independently selected from the group consisting of an oxygen atom, a1, 1 '-carbonyl group, a methylene group and substituted forms thereof, a1, 2-ethylene group and substituted forms thereof, a1, 1' -vinyl group and substituted forms thereof, and b is 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (

Can be linked to form a ring, on different atoms

Can also be linked to form a ring, where K is preferred₁And K₂K to₃And K₄K to₅And K₆C to₁And C₂C to₃And C₄C to₅And C₆Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not; wherein, K₁And K₂K to₃And K₄K to₅And K₆The ring formed between preferably has the following structure:

C₅and C₆The ring formed between preferably has the following structure:

among them, the force sensitive group of the general formula 3-I-1 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e₁、E₂Each independently selected from any one of the following structures:

a typical structure of the formula 3-I-1 can be exemplified as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r₁Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r₀Each independently selected from the group consisting of: -H, -CH₃、-F、-Cl、-Br、-COOH、-CN、

R, R at different locations₀May be the same or different;

among them, the force sensitive group of the general formula 3-I-2 is preferably selected from at least a subset of the following general structures:

wherein E is₁、E₂Each independently selected from any one of the following structures:

a typical structure of the general formula 3-I-2 can be exemplified as follows:

R, R at different locations₀May or may not be the sameThe same is carried out;

among them, the force sensitive groups of formula 3-I-3 are preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e is selected from any one of the following structures:

typical structures of the general formula 3-I-3 can be exemplified as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r₀Each independently selected from the group consisting of: -H, -CH₃、-F、-Cl、-Br、-COOH、-CN、

R, R at different locations₀May be the same or different;

among them, the force sensitive groups of the general formula 3-I-4 are preferably selected from at least a subset of the following general structures:

wherein E is selected from any one of the following structures:

typical structures of the general formula 3-I-4 can be exemplified as follows:

R, R at different locations₀Can be the same as orMay be different;

among them, the force sensitive groups of the general formula 3-I-5 are preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

typical structures of the general formula 3-I-5 can be exemplified as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r₁、R₂、R₃Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions can be the same or different;

among them, the force sensitive groups of the general formula 3-I-6 are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-I-6 can be exemplified as follows:

among them, the force sensitive groups of the general formulae 3-I-7 are preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e is selected from any one of the following structures:

f is selected from any one of the following structures:

typical structures of the general formulae 3 to I-7 can be illustrated as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r₁Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r₀Selected from the following groups: -H, -CH₃、-F、-Cl、-Br、-COOH、-CN、

R at different positions can be the same or different;

among them, the force sensitive groups of the general formula 3-I-8 are preferably selected from at least a subset of the following general structures:

wherein E is selected from any one of the following structures:

f is selected from any one of the following structures:

typical structures of the general formulae 3 to I-8 can be illustrated as follows:

R at different positions can be the same or different;

among them, the force sensitive groups of the general formula 3-I-9 are preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; g is selected from any one of the following structures:

typical structures of the general formulae 3 to I-9 can be illustrated as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r at different positions can be the same or different; r₁Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues;

among them, the force sensitive groups of the general formula 3-I-10 are preferably selected from at least a subset of the following general structures:

wherein G is selected from any one of the following structures:

typical structures of the general formula 3-I-10 can be exemplified as follows:

among them, the force sensitive groups of the general formula 3-I-11 are preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; f is selected from any one of the following structures:

typical structures of the general formula 3-I-11 can be exemplified as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions can be the same or different;

among them, the force sensitive groups of the general formula 3-I-12 are preferably selected from at least a subset of the following general structures:

wherein, F is selected from any one of the following structures:

typical structures of the general formulae 3 to I-12 can be illustrated as follows:

wherein each R is independently selected from any one of the following structures: hydrogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residueR is more preferably a hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, or pyridyl group, and is more preferably a hydrogen atom, fluorine atom, cyano group, methyl group, or phenyl group; r₁、R₂Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions may be the same or different.

In the invention, the covalent single force sensitive group of DA series, hybrid DA series and light-operated DA series reverse cyclization mechanism can also carry out reverse cyclization reaction through thermal activation so as to dissociate the force sensitive group.

In the present invention, the covalent single force sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism refers to a single force sensitive group containing [4+4] cycloaddition force sensitive elements, and the structural general formula thereof includes but is not limited to the following classes:

wherein the content of the first and second substances,

the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, an aza-benzene, an aza-naphthalene, an aza-anthracene or a substituted form of the above groups; i is₆～I₁₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;

Can be linked to form a ring, on different atoms

Or linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof;

among them, the force sensitive group of formula 3-J-1 is preferably selected from at least a subset of the following general structures:

wherein R is₁、R₂、R₃、R₄Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

a typical structure of the formula 3-J-1 can be exemplified as follows:

among them, the force sensitive group of formula 3-J-2 is preferably selected from at least a subset of the following general structures:

a typical structure of the formula 3-J-2 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-3 are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-3 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-4, which are preferably selected from a subset of the following general structures:

typical structures of the general formula 3-J-4 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-5, which are preferably selected from a subset of the following general structures:

typical structures of the general formula 3-J-5 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-6, which are preferably selected from a subset of the following general structures:

typical structures of the general formula 3-J-6 can be exemplified as follows:

wherein R is₁Is selected fromA structure of: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

among them, the force sensitive groups of formula 3-J-7 are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-7 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-8 are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-8 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-9, which are preferably selected from at least a subset of the following general structures:

among them, the force sensitive groups of formula 3-J-10, which are preferably selected from at least a subset of the following general structures:

among them, the force sensitive groups of formula 3-J-11 are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-11 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-12, which are preferably selected from a subset of the following general structures:

among them, the force sensitive groups of formula 3-J-13, which are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-13 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-14 are preferably selected from at least a subset of the following general structures:

among them, the force sensitive groups of formula 3-J-15 are preferably selected from at least a subset of the following general structures:

among them, the force sensitive groups of formula 3-J-16, which are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-16 can be exemplified as follows:

among them, the force sensitive groups of formula 3-J-17, which are preferably selected from at least a subset of the following general structures:

typical structures of the general formula 3-J-17 can be exemplified as follows:

in the invention, the covalent single force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also carry out reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force-sensitive group.

In the present invention, covalent single force sensitive groups based on the electrocyclization mechanism include, but are not limited to, the following series: six-membered ring series, five-membered ring series, three-membered ring series.

In the present invention, the covalent single force sensitive group of the six-membered ring series electrical cyclization mechanism refers to a single force sensitive group containing six-membered ring force sensitive elements, and the structural general formula includes but is not limited to the following groups:

wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R and nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain, whether or not participating in force activation, different on the same atom

Can be linked to form a ring, on different atoms

Or can be connected into a ring. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

The six-membered ring monomer containing the general structural formula (4-A-1) of the present invention is further preferably selected from, but not limited to, the following structures:

wherein, X₁Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from an oxygen atom; y is₁Each independently selected from C-R, nitrogen atom; z₁Is selected from C- (R)₂Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)₂A nitrogen atom; z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂Nitrogen atom, preferably C- (R)₂A nitrogen atom; when Z is₁Or Z₂Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)₂When connected to it

The number is 0;

an aromatic ring having an arbitrary number of elements; n is a total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the ring-constituting atoms, and is 0, 1 or an integer X, Y, R greater than 1,

The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.

In the present invention, the six-membered ring monomer having the general structural formula (4-A-1) is exemplified by the following structures:

wherein, X, X₁、X₂、X₃、Y、Y₁The selection range of R is as described in the series of force-sensitive groups, and is not described in detail herein;

each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.

The six-membered ring monomer containing the general structural formula (4-A-2) of the present invention is further preferably selected from, but not limited to, the following structures:

wherein, X, R, Z₁、Z₂、

n、

In the present invention, the six-membered ring monomer having the general structural formula (4-A-2) is exemplified by the following structures:

wherein the content of the first and second substances,

The six-membered ring monomer containing the general structural formula (4-A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein X, M,

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted.

In the present invention, the six-membered ring monomer having the general structural formula (4-A-3) is exemplified by the following structures:

wherein the content of the first and second substances,

The six-membered ring monomer containing the general structural formula (4-A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein, X, Y, Z₁、Z₂、

The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.

In the present invention, the six-membered ring monomer having the general structural formula (4-A-4) is exemplified by the following structures:

wherein, the selection range of X, Y is as described in the series of force-sensitive groups, and is not described in detail herein;

The six-membered ring monomer containing the general structural formula (4-A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein the content of the first and second substances,

In the present invention, the six-membered ring monomer having the general structural formula (4-A-5) is exemplified by the following structures:

wherein the content of the first and second substances,

The six-membered ring monomer containing the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein X, R,

n、

The six-membered ring monomer having the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein R is,

In the present invention, the six-membered ring monomer having the general structural formula (4-A-6) is exemplified by the following structures:

wherein, the selection range of X is as the previous description of the series of force-sensitive groups, and the description is omitted;

The six-membered ring monomer containing the general structural formula (4-A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:

wherein, X, Z₂、

In the present invention, the six-membered ring monomer having the general structural formula (4-A-7) is exemplified by the following structures:

wherein the content of the first and second substances,

independently of each other and with the polymer chain or the supramolecule involved in the force activationThe subpolymer chains are linked.

In the invention, the covalent single force sensitive group of the five-membered ring series electrical cyclization mechanism is a force sensitive group containing five-membered ring force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:

wherein A is₀Is selected from

A₁Is selected from

A₂Is selected from

Wherein the structure represented by the general formula 4-B-1 is preferably selected from the following general structures:

wherein, T₁Each independently of the other being a substituent group, preferably an electron-withdrawing group, and two T' s₁Can be connected to form a ring;

wherein the content of the first and second substances,

is a conjugated ring structure or a heterocyclic ring structure containing double bonds; position 1 is attached to a force-activatable bond and position 2 is attached to another linking atom of the five-membered ring; n is

Is 0, 1 or an integer greater than 1, m is the number of R therein, which is 0, 1 or an integer greater than 1; wherein, the ring-forming atom at the 1-position side and

the ring-forming atoms on the side of the position 2 and the ring-forming atoms on the symmetry axis shown by the dotted line are connected with R; the ring structure is preferably

Because the sensor is sensitive to light at the same time, double response of force and light can be realized;

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;

specifically, the typical structure of the formula 4-B-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Among them, the force sensitive group of the general formula 4-B-2 is further preferably selected from the following general structure:

wherein A is₀、

The definition and the selection range of the formula (I) are the same as those of the general formula 4-B-2;

is a positively charged conjugated ring structure or heterocyclic structure, wherein n is

The total number of (a) is 0, 1 or an integer greater than 1;

is an aromatic ring structure, n is

The total number of (a) is 0, 1 or an integer greater than 1;

is a conjugated ring structure or a heterocyclic ring structure with strong electron-withdrawing groups and/or heteroatoms, n is

The total number of (a) is 0, 1 or an integer greater than 1;

is a conjugated ring structure or a conjugated heterocyclic structure, n is

The total number of (a) is 0, 1 or an integer greater than 1;

specifically, the typical structure of the formula 4-B-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

independently of one another and participating in force activationPolymer chains or supramolecular polymer chains.

Among them, the structure represented by the general formulae 4-B-3 to 4-B-6 is more preferably the following general formula:

wherein E is₁Each independently selected from one of two structures shown below:

wherein the content of the first and second substances,

each independently is an aromatic ring structure, n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1; e₂Are any suitable atoms (including hydrogen atoms), substituents, and substituted polymer chains, with or without participation in force activation, preferably E₁(ii) a In the same structure, when E₂Is selected in the range of E₁When E is greater₁And E₂Are independent of each other; a. the₁The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; t is₂Each independently a substituent group, preferably an electron-withdrawing group, and two T's in the general formulae 4-B-4-1, 4-B-6-1₂Can be connected to form a ring;

is a heterocyclic ring containing at least one nitrogen atom, A_xIs a carbon atom or a nitrogen atom, and n is a ring member attached to a heterocyclic ring

The total number of (a) is 1 or an integer greater than 1;

is an aromatic ring structure, each R is independently selected from any suitable atom (including a hydrogen atom), substituent, non-participating in a force or activityA substituted polymer chain; n is the total number of R numbers, and is 0, 1 or an integer more than 1; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;

In one embodiment of the present invention, the force-sensitive element is preferably connected with some specific structures to realize a structure responding to specific metal ions, so that the force-sensitive group has ion detection function besides force response. By way of example, typical structures that can achieve a response to a particular metal ion are listed below, but the invention is not limited thereto:

Cu²⁺：

Hg²⁺：

Fe³ ⁺：

wherein each X is independently selected from

Each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

In another embodiment of the present invention, the force-sensitive element is preferably a structure capable of chelating with metal ions and achieving force-induced ion release, and exemplary structures capable of chelating with metal ions and achieving force-induced ion release are listed below, but the present invention is not limited thereto:

wherein each X is independently selected from

In another embodiment of the present invention, the force-sensitive moiety is preferably a structure that can be linked to an energy receptor and that can effect energy transfer upon force activation; by way of example, typical structures that can be attached to an energy receptor and that can effect energy transfer upon force activation are as follows, but the invention is not limited thereto:

wherein L is any suitable covalent linking group having a length of less than 10 nm; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

each independently of any suitable atom (including hydrogen), substituent, and with or without participation in force activationThe substituted polymer chains are linked.

Specifically, other typical structures shown in the general formula 4-B-3 are exemplified below, but the present invention is not limited thereto:

wherein A is₁The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; each X is independently selected from

Specifically, the typical structure shown in the general formula 4-B-4 is exemplified as follows, but the present invention is not limited thereto:

wherein each X is independently selected from

Specifically, the typical structure shown in the formula 4-B-5 is exemplified as follows, but the present invention is not limited thereto:

wherein each X is independently selected from

Specifically, the typical structure shown in the general formula 4-B-6 is exemplified as follows, but the present invention is not limited thereto:

wherein each X is independently selected from

Are independent of each other and participate in physical activitiesLinked by chemical substituted polymer chains or supramolecular polymer chains.

Wherein the structure represented by the general formula 4-B-7 is preferably selected from at least a subset of the following general structures:

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; e₁、E₂The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3-1;

is an aromatic ring structure, is a linking position, wherein position 1 is linked to a carbon atom and position 2 is linked to an oxygen atom; wherein the ring-forming atom at the 1-position side and the ring-forming atom on the axis of symmetry indicated by the dotted line are bonded to R, and the ring-forming atom at the 2-position side and

connecting; n is the total number of R's bonded to the atoms constituting the aromatic ring, and m is

The total number of the number; t is₃Each independently selected from one of two structures shown below:

two T in the same type₃When selected from the same structure, T₃The specific structures of the components can be the same or different; wherein the content of the first and second substances,

each independently is an aromatic ring structure, and n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1.

Specifically, typical structures of the formula 4-B-7 are exemplified below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the spiro force-sensitive group can regulate and control heat, light and force-induced activation and generate coordination under the existence of metal ions, protons and other ligands, thereby regulating and controlling the performances of thermochromism, photochromism, photocrosslinking, mechanochromism, force-induced crosslinking and the like; by designing and adjusting the substituent of the spiro force sensitive group, particularly the coordination or the substituent containing the coordination group, the coordination of the activated spiro force sensitive group and ligands such as metal ions and the like, such as coordination number, coordination strength, optical characteristics, catalytic characteristics and the like, can be further regulated and controlled, and more extensive and adjustable photoinduced, thermotropic and force-induced properties and the like can be obtained.

In the present invention, the covalent single force-sensitive group of the electrical cyclization mechanism of the three-membered ring series refers to a force-sensitive group containing three-membered ring (including three-membered ring and four-membered/five-membered ring) force-sensitive elements, and the structural general formula includes but is not limited to the following groups:

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; a is selected from-O-, -S-),

Wherein, each E is independently selected from hydrogen atom, halogen atom, alkyl and alkoxy.

Wherein, the structure represented by the general formula 4-C-1-1 is further preferably selected from the following general structures:

wherein E is_XEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

a typical structure of the formula 4-C-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the alkyne-furan adduct series refers to a force-sensitive group containing alkyne-furan adduct force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:

wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;

A typical structure of the formula 5-A-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the anthracene-triazoline-dione adduct series refers to a force-sensitive group containing anthracene-triazoline-dione adduct force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the force sensitive group is generated after force activationThe anthracene group has a fluorescence effect, can realize special effects including but not limited to force-induced fluorescence and the like, and is preferably connected with other functional groups with a fluorescence enhancement effect, so that the force-induced fluorescence effect is more remarkable; the triazolinedione group generated after the force-sensitive group is activated by force can be subjected to addition reaction with groups such as diene group and the like, and when R is a substituted polymer chain which does not participate in the force activation or is connected with the triazolinedione group in another force-sensitive group and the system simultaneously contains the groups such as diene group and the like, special effects including but not limited to force-induced chemical reaction, force-induced crosslinking enhancement and the like can be realized, so that the triazolinedione group is also preferable.

A typical structure of the formula 5-B-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of the alkynyl series bending activation mechanism refers to a force sensitive group containing alkynyl force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following:

wherein the content of the first and second substances,

each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation; after being bent and activated, the series of force sensitive groups can generate azide-alkyne click reaction without catalysts with azide groups, and special effects including but not limited to force-induced crosslinking and the like are realized.

A typical structure of the formula 5-C-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the covalent single force sensitive group of the bending activation mechanism of the azophenyl series refers to a force sensitive group containing azophenyl force sensitive elements, and the structural general formula includes but is not limited to the following:

wherein the content of the first and second substances,

each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the series of force sensitive groups can generate phase change after being activated by bending, and achieve special effects including but not limited to force-induced softening and the like.

A typical structure of the formula 5-D-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, covalent single force sensitive groups based on other mechanisms include, but are not limited to, the following series: a double nitrite series, a1, 1' -linked condensed ring series, a dithiomaleimide series and a Michael reaction series.

In the invention, the covalent single force-sensitive group of the other mechanism of the double-nitrite series refers to a single force-sensitive group containing a double-nitrite force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following groups:

wherein X is selected from oxygen atom, sulfur atom, preferably oxygen atom;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

In the present invention, the structure of the covalent single-force sensitive group of the other mechanism of the double nitrite series can be exemplified as follows:

wherein;

In the invention, the covalent single force sensitive group of other mechanisms of the 1, 1 '-linked condensed ring series refers to a single force sensitive group containing 1, 1' -linked condensed ring force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:

wherein each R is independently any suitable atom, substituent, substituted polymer chain;

an aromatic ring having an arbitrary number of elements; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the aromatic ring-forming atom may be substituted with an optional substituent or may be unsubstituted; it may be a monocyclic structure, a polycyclic structure, or a fused ring structure.

In the present invention, the structure of the covalent single force sensitive group of the other mechanism of the 1, 1' -linked condensed ring series can be exemplified as follows:

wherein the content of the first and second substances,

In the present invention, the covalent single force-sensitive group of the dithiomaleimide series with other mechanisms refers to a single force-sensitive group containing a dithiomaleimide force-sensitive element, and the structural general formula includes but is not limited to the following groups:

wherein the content of the first and second substances,

In the present invention, the structure of the covalent single force sensitive group of the bis-thiolylimide series with other mechanisms can be exemplified as follows:

wherein the content of the first and second substances,

In the invention, the covalent single force sensitive group of other mechanism of the Michael reaction series refers to a single force sensitive group containing a Michael reaction force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following classes:

wherein the content of the first and second substances,

rings representing arbitrary numbers of elements, on said rings

Is attached to the ring by the Michael reaction;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different. Under the action of mechanical force, a covalent single-force sensitive group of other mechanisms of the Michael reaction series can pull one amido bond away and form an amido bond and a carboxyl group after ring opening.

In the present invention, the structure of the covalent single force sensitive group of the other mechanism of the Michael reaction series can be exemplified as follows:

in the present invention, the division is performed in a non-covalent complexing manner, and the non-covalent single force-sensitive groups used to generate the complex force-sensitive groups include, but are not limited to, the following groups: non-covalent single force sensitive groups based on supramolecular complexes, non-covalent single force sensitive groups based on supramolecular assemblies, non-covalent single force sensitive groups based on aggregates, non-covalent single force sensitive groups based on compositions. Non-covalent single force-sensitive groups based on a non-covalent single force-sensitive group of supramolecular complexes and a composition of motifs are preferred as force-sensitive components in a complex force-sensitive group for generating complexes containing non-covalent force-sensitive components. The non-covalent single force sensitive group is capable of specifically responding to mechanical forces and producing significant specific force-induced response properties/effects, such as catalytic, optical, spectroscopic, etc. supramolecular interactions.

In the present invention, the non-covalent single force sensitive groups based on supramolecular complexes include, but are not limited to, the following series: coordination bond series, host-guest interaction series, hydrogen bond interaction series and pi-pi stacking interaction series.

In the present invention, non-covalent single force-sensitive groups based on coordination bonds include, but are not limited to, the following sub-series: complexation of unsaturated carbon-carbon bonds with transition metals, carbene-metal coordination bonds, boron-nitrogen coordination bonds, platinum-phosphorus coordination bonds, metallocene coordination bonds, and ligand-lanthanide metal ion complexation.

In the present invention, the non-covalent single force sensitive group of the complexation of the unsaturated carbon-carbon bond and the transition metal refers to a single force sensitive group containing a complexation force sensitive element of the unsaturated carbon-carbon bond and the transition metal, and the structural general formula thereof includes but is not limited to the following types:

wherein the content of the first and second substances,

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each R is independently any suitable atom, substituent, substituted polymer chain; in different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.

The structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-1) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-2) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-3) and the transition metal of the present invention is exemplified by the following:

the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-5) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-6) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-7) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-8) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-9) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-10) and the transition metal of the present invention is exemplified by the following:

the structure of the complex of the unsaturated carbon-carbon bond having the general structural formula (A-11) and the transition metal of the present invention is exemplified by the following:

in the invention, the non-covalent single force sensitive group of the carbene-metal coordination bond refers to a single force sensitive group containing a carbene-metal coordination bond force sensitive element, and the structural general formula of the single force sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

In the present invention, the carbene-metal coordination bond, carbene ligand, is further preferably selected from, but not limited to, the following structures:

wherein, X₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C- (R)₂Preferably from an oxygen atom;

the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.

In the present invention, the carbene-metal coordination bond having the general structural formulas (B-1), (B-2), (B-3) and (B-4) can be selected from, but not limited to, the following structures:

wherein, X₄、

The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted; m is a metal center, which may be any suitable ionic form, compound/chelate form, and combinations thereof, of any one of the transition metals; .

In the present invention, the carbene-metal coordination bond having the general structural formulae (B-1), (B-2), (B-3) and (B-4) has the following structure:

Wherein, X₄、M、

In the present invention, the non-covalent single force-sensitive group of boron-nitrogen coordination bond refers to a single force-sensitive group containing a force-sensitive element of boron-nitrogen coordination bond, and the structural formula thereof includes but is not limited to the following types:

wherein the content of the first and second substances,

The boron-nitrogen coordination bond of the present invention, formula (C-1), may further preferably be selected from, but not limited to, at least one of the following structures:

wherein the content of the first and second substances,

r, n, the ranges of choice are as previously described in the series of force-sensitive clusters and will not be further described herein;

represents any number of nitrogen heterocycles, including but not limited to aliphatic nitrogen heterocycles, aromatic nitrogen heterocycles, and combinations thereof.

In the present invention, said boron-nitrogen coordination bond having the general structural formula (C-1) is further preferably selected from, but not limited to, the following structures:

in the present invention, the boron-nitrogen coordination bond having the general structural formula (C-1) is exemplified by the following structures:

in the present invention, the non-covalent single force-sensitive group of platinum-phosphorus coordination bond refers to a single force-sensitive group containing platinum-phosphorus coordination bond force-sensitive elements therein, and the structural formula thereof includes but is not limited to the following types:

wherein, X₅Each independently selected from a chlorine atom, a bromine atom, an iodine atom, preferably from a chlorine atom;

In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following subclasses:

wherein, X₅、

In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following structures:

wherein, X₅、

In the present invention, the structure of the platinum-phosphorus coordination bond having the general structural formula (D-1) is exemplified as follows:

in the present invention, the non-covalent single force-sensitive group of metallocene coordination bond refers to a single force-sensitive group containing a force-sensitive element of metallocene coordination bond, and the structural formula thereof includes but is not limited to the following types:

wherein, M is a metal center,

is a ligand of cyclopentadiene and a ligand of cyclopentadiene,

the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted. The metal centers are preferably metals of the first to seventh subgroups and of the eighth group. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). The metal center is more preferably a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the third subgroup (Sc, Y), a metal of the fourth subgroup (Ti, Zr), a metal of the fifth subgroup (V, Nb), a metal of the sixth subgroup (Cr, Mo), a metal of the seventh subgroup (Mn, Tc), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanoid series (La, Eu, Tb, Ho, Tm, Lu), a metal of the actinide series (Th). More preferably Cu, Zn, Fe, Co, Ni, Zr, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, and still more preferably Fe, Co, Ni, Zr.

In the present invention, the metallocene coordination bond having the general structural formula (E-1) is exemplified by the following structures:

wherein the content of the first and second substances,

In the invention, the non-covalent single force sensitive group of ligand-lanthanide metal ion complexation refers to a single force sensitive group containing a ligand-lanthanide metal ion complexation force sensitive element, and the single force sensitive group can change the position of the ligand group more easily when being stressed, thereby showing obvious stress response properties, including changes of fluorescence, color and the like.

In embodiments of the present invention, suitable ligand groups may be exemplified by, but are not limited to:

in an embodiment of the invention, the lanthanide metal includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; preferably lanthanide series Ce, Eu, Tb, Ho, Tm, Lu; more preferably Ce, Eu, Tb, to obtain more remarkable stress responsiveness.

In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the non-covalent single force sensitive groups based on supramolecular assemblies include, but are not limited to, the following series: the dye molecule series non-covalent single force sensitive group comprises a donor-acceptor series, a diketopyrrolopyrrole series, a conjugated series, a platinum coordination series, a gold coordination series, a beryllium coordination series, a copper coordination series, an iridium coordination series, a boron coordination series, a phenothiazine series, a dioxaborolane series and a dye molecule series.

In the present invention, the non-covalent single force-sensitive group of the donor-acceptor series refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by a donor-acceptor self-assembly element, and the structural general formula thereof includes but is not limited to the following classes:

wherein W is an atom or group having an electron withdrawing effect; wherein, the atom with electron-withdrawing effect is selected from but not limited to oxygen atom or sulfur atom, preferably oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:

wherein Ar is₁、Ar₂Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a polycyclic structure or a fused ring structure; by way of example, suitable Ar' s₁、Ar₂Selected from, but not limited to:

wherein the content of the first and second substances,

A typical structure of the formula F-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

A typical structure of the formula F-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

A typical structure of the formula F-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the non-covalent single force-sensitive group of the diketopyrrolopyrrole series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by diketopyrrolopyrrole self-assembly elements, and the structural general formula of the non-covalent single force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

each independently of any suitable atom (including hydrogen), substituent, andthe substituted polymer chains, with or without participation in force activation, are linked.

A typical structure of the formula G-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the conjugated series of non-covalent single force-sensitive groups refer to force-sensitive groups containing self-assembled aggregate force-sensitive elements formed by conjugated self-assembled elements; wherein, the conjugated self-assembly motif includes but is not limited to the following subseries: polydiacetylene series, polydiphenylacetylene series, polythiophene series, polypyrrole series, anthraquinone series, polyfluorene series, oligomeric p-phenylene vinylene series, bis (benzoxazole) stilbene series, and aza-condensed ring sub-series self-assembly motif.

Wherein, the structural general formula of the polydiacetylene subunit self-assembly unit includes but not limited to the following types:

wherein n is the number of the repeating units, and the value range of n is an integer greater than 2, preferably an integer greater than or equal to 5, and more preferably an integer greater than or equal to 10;

A typical structure of the formula H-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein n and p are the number of the repeating units, and the value ranges thereof are respectively independent integers more than 2, preferably more than or equal to 5, and more preferably more than or equal to 10;

Wherein, the structural general formula of the polydiphenylacetylene self-assembly motif comprises but is not limited to the following types:

wherein n is,

The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.

A typical structure of the formula H-2 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of the repeating units is an integer which is greater than 2, preferably greater than or equal to 5, and more preferably greater than or equal to 10;

Wherein, the structural general formula of the sub-series self-assembly motif of the polythiophene comprises but is not limited to the following classes:

wherein n is the number of the repeating units and the value range of n is an integer larger than 5;

A typical structure of the formula H-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of repeating units is an integer in the range of greater than 5.

Wherein, the structural general formula of the self-assembly motif of the polypyrrolidine series includes but is not limited to the following classes:

wherein n is,

The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.

A typical structure of the formula H-4 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of repeating units is an integer with a value range of more than 5;

Wherein, the structural general formula of the self-assembly motif of the anthraquinone sub-series includes but is not limited to the following classes:

wherein n is,

The definition, selection range and preferred range are the same as those of the general formula H-3.

A typical structure of the formula H-5 can be exemplified as follows, but the present invention is not limited thereto:

wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-5;

Wherein, the structural general formula of the polyfluorenesub-series self-assembly motif includes but is not limited to the following classes:

wherein n is,

A typical structure of the formula H-6 can be exemplified as follows, but the present invention is not limited thereto:

wherein n, n₁、n₂The number of the repeating units is defined, and the value ranges of the repeating units are respectively independent integers more than 5;

Wherein, the structural general formula of the self-assembly unit of the oligomeric p-phenylene vinylene subunit includes but is not limited to the following types:

wherein n is,

A typical structure of the formula H-7 can be exemplified as follows, but the present invention is not limited thereto:

wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-7;

Wherein, the structural general formula of the bis (benzoxazole) stilbene sublines self-assembly motif includes but is not limited to the following classes:

wherein the content of the first and second substances,

selected from, but not limited to, at least one of the following structures:

A typical structure of the formula H-8 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

Wherein, the structural general formula of the self-assembly motif of the aza-condensed ring sub-series includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula H-9 can be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the platinum coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by platinum coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein each V is independently selected from a carbon atom or a nitrogen atom;

wherein Lg is₁Is a monodentate ligand coordinated to the platinum atom; wherein the monodentate ligand is selected from, but not limited to: a halogen atom,

Wherein Lg is₂Is a monodentate ligand coordinated to the platinum atom; each Lg₂Are the same or different; wherein the monodentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a bidentate ligand with V and nitrogen atoms as coordinating atoms; by way of example, the bidentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a tridentate ligand with V and nitrogen atoms as coordination atoms; by way of example, the tridentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

is a tetradentate ligand taking V and nitrogen atoms as coordination atoms; by way of example, the tetradentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

Typical structures of the formulae I-1 to I-4 may be illustrated below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the gold coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by gold coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein Lg is₃Is a monodentate ligand coordinated to a gold atom; each Lg₃Are the same or different; wherein the monodentate ligand is selected from, but not limited to:

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited and is selected from, but not limited to, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom; the hydrogen atoms on the ring-forming atoms may be substituted with any suitable substituent atom or substituent; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. By way of example, those that are suitable

wherein the content of the first and second substances,

the definition, selection range and preferable range of the formula (I) are the same as those of the general formula (I-2);

wherein the content of the first and second substances,

is a bidentate ligand with a sulfur atom and a nitrogen atom as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

is a bidentate ligand taking a phosphorus atom as a coordination atom, wherein, the metal atoms coordinated with phosphine can be the same gold atom or different gold atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

Typical structures of formulae J-1 to J-7 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the beryllium coordinated series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembled aggregate force-sensitive elements formed by beryllium coordinated self-assembled elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

A typical structure of the formula K-1 can be illustrated as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the copper coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by copper coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein the content of the first and second substances,

A typical structure of the formula L-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the iridium coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by iridium coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein the content of the first and second substances,

is a bidentate ligand with carbon atoms and nitrogen atoms as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

is a bidentate ligand with nitrogen atoms as coordination atoms; by way of example, those that are suitable

wherein the content of the first and second substances,

A typical structure of the formula M-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the boron coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by boron coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein, R is respectively and independently selected from halogen atom, cyano-group and C_1-10Hydrocarbyl/heterohydrocarbyl, substituted C_1-10Hydrocarbyl/heterohydrocarbyl; r is preferably selected from halogen atoms, phenyl, pentafluorophenyl; v, V' are each independently selected from an oxygen atom or a nitrogen atom;

each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, of any two of the same general formula

Cyclopentadiene rings or no rings.

Wherein the structures represented by the general formulae N-1 to N-5 are preferably selected from at least a subset of the following general structures:

wherein the content of the first and second substances,

is an aromatic ring; a ring junction of the aromatic ringThe structure is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the content of the first and second substances,

to connect n

The ring-forming atoms of the ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms; wherein the content of the first and second substances,

to connect n

At least one of the ring-forming atoms of the nitrogen-containing aromatic heterocyclic ring is a nitrogen atom, the nitrogen-containing aromatic heterocyclic ring forms a coordinate bond with a boron atom through the nitrogen atom, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms; wherein the content of the first and second substances,

to connect n

At least two of the ring-forming atoms of (1) are carbon atoms, and the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; wherein the content of the first and second substances,

to connect n

At least two of the ring-forming atoms of the nitrogen-containing aromatic heterocycle of (1) are nitrogen atoms, and one of the nitrogen atoms forms a nitrogen atom with a boron atomCoordinate bonds, and the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms;

wherein R, V, V

The definitions, selection ranges and preferred ranges of the general formulas N-1 to N-5 are the same.

Typical structures of the formulae N-1 to N-5 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the phenothiazine series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive units formed by phenothiazine self-assembly units; wherein, the phenothiazine self-assembly motif comprises but is not limited to the following classes:

wherein each R is independently selected from the group consisting of atoms (including hydrogen atoms), substituents, and substituted polymer chains that may or may not participate in force activation; wherein said substituent atoms are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom; the substituent is preferably selected from substituents with electron-withdrawing effect, so that the intermolecular stacking effect is enhanced, and more remarkable force-induced responsiveness is obtained; wherein said substituents having electron withdrawing effect include but are not limited to: trifluoromethyl, trichloromethyl, nitro, cyano, sulfonic group, aldehyde group, alkyl acyl, alkoxy acyl, carboxyl, amide group;

wherein n is the total number of substituent atoms, substituents, and substituted polymer chains linked to the atoms constituting the ring structure, and is 0, 1, or an integer greater than 1; when n is more than 1, the structures of the R can be the same or different;

wherein the content of the first and second substances,

Typical structures of the general formulae O-1, O-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the non-covalent single force-sensitive group of the dioxaborolane series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by self-assembly elements of the dioxaborolane, and the structural general formula of the non-covalent single force-sensitive group comprises the following groups:

wherein Ar is an aromatic ring having an electron donating effect; wherein the aromatic ring is a polycyclic structure selected from, but not limited to:

wherein the content of the first and second substances,

A typical structure of the formula P-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the non-covalent single force-sensitive group of the dye molecule series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by dye molecule self-assembly elements; wherein, the dye molecule self-assembly motif is selected from one of the following structural formulas:

wherein the hydrogen atoms on the dye molecules may be substituted or unsubstituted by any suitable atom, substituent, polymer chain; and the dye molecules are linked to the polymer or supramolecular polymer chains by suitable means.

By way of example, the structure of a typical self-assembly motif of a dye molecule is shown below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, non-covalent, single force-sensitive groups based on aggregates include, but are not limited to, the following series: divinylanthracene series, tetraarylethylene series, cyanoethylene series, berberine series, maleimide series, 4-hydropyran series non-covalent single force sensitive groups.

In the invention, the divinylanthracene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by divinylanthracene aggregation-induced emission elements, and the general structural formula of the group includes but is not limited to the following types:

wherein Ar is₁、Ar₂Each independently selected from aromatic rings, the ring structure of which is selected from monocyclic structure, polycyclic structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

Typical structures of the formulae Q-1 to Q-3 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the non-covalent single force-sensitive group of the tetraarylethylene series refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by tetraarylethylene aggregation-induced emission elements, and the structural general formula includes but is not limited to the following classes:

wherein each W is independently selected from a direct bond,

Wherein Ar is₁、Ar₂、Ar₃、Ar₄Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; wherein the substituted atom, the substituent, the substituted polymer chain are not particularly limited; in order to increase steric hindrance and aggregation-induced emission of the luminescent moiety in a non-planar conformation, and to form loosely-packed aggregates, so as to obtain a more significant force-induced response effect, the ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be adjusted in a large range can be obtained, and the use requirements of various application scenes can be met; in order to increase the intramolecular charge transfer property and obtain a more significant force-induced response effect, particularly a force-induced response effect with a significant change in fluorescence wavelength shift and a high force-induced color contrast, it is more preferable that the substituent on the aromatic ring structure is a substituent having a strong electron-donating effect or electron-withdrawing effect;

wherein the content of the first and second substances,

Typical structures of the formulae R-1 to R-7 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the cyanoethylene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by cyanoethylene aggregation-induced emission elements, and the structural general formula of the group includes but is not limited to the following classes:

wherein Ar is₁、Ar₂Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; the substituent atom, substituent group, and substituted polymer chain are not particularly limited. In order to increase steric hindrance and aggregation-induced emission of the luminescent moiety in a non-planar conformation, and to form loosely-packed aggregates, so as to obtain a more significant force-induced response effect, the ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by rational selection of multiple ringsThe structure and the condensed ring structure can also regulate and control the spectral properties of the formed force sensitive groups in a large range so as to obtain adjustable color change and fluorescence/phosphorescence emission wavelength in a large range and meet the application requirements of various application scenes; in order to obtain more significant force-responsive effects, especially force-responsive effects with significant shift in fluorescence wavelength and high color contrast of force-induced discoloration, it is preferred that a portion of the hydrogen atoms on the aromatic ring be substituted with a heteroatom, a hydrocarbyl substituent, or a heteroatom substituent, by way of example, suitable heteroatoms, hydrocarbyl substituents, heteroatom substituents are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, pentafluorothio group, nitro group, cyano group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20Alkylamino radical, C_1-20Aryloxy radical, C_1-20Arylthio radical, C_1-20An arylamine group. Ar is₁、Ar₂Preferably at least one of the following structures, but the invention is not limited thereto:

by way of example, typical Ar₁、Ar₂Including but not limited to one or more of the following structures:

wherein Ar is₃Is a divalent aromatic ring, the structure of which is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms bonded to the ring-forming atoms are substituted with any suitable substituent atom, substituent group, or substituted polymer chainOr is unsubstituted; wherein the substituent atom is preferably selected from fluorine atom, chlorine atom, bromine atom and iodine atom, and the substituent group is preferably selected from C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Alkoxy radical, C_1-20Alkylthio radical, C_1-20Alkylamino radical, C_1-20Aryloxy radical, C_1-20Arylthio radical, C_1-20An arylamine group. Ar is₃Preferably at least one of the following structures, but the invention is not limited thereto:

by way of example, typical Ar₃Including but not limited to one or more of the following structures:

wherein the content of the first and second substances,

Wherein the structure represented by the general formula S-1 is further preferably selected from the following general structures:

wherein Ar is₄Definition, selection range, preferred range of (1) and Ar₁(ii) a Wherein Ar is₁、Ar₂、

The definition, selection range and preferable range of (A) are the same as those of the general formula S-1.

Typical structures of the formulae S-1 to S-4 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the berberine series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by berberine aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:

wherein a is an integer of 1-5, preferably 1 or 2;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group, preferably from substituent group with electron-donating effect;

wherein R is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect;

wherein the content of the first and second substances,

A typical structure of the formula T-1 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, the maleimide series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive element formed by maleimide aggregation-induced emission element, and its structural general formula includes but is not limited to the following classes:

wherein R is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect; by way of example, said atoms or substituents having an electron-withdrawing effect are selected from, but not limited to: halogen atom, nitro group, pentafluorothio group, trifluoromethyl group, 4-trifluoromethyl-phenyl group;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or greater than 1An integer number; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

Typical structures of the general formulae U-1, U-2 may be exemplified as follows, but the present invention is not limited thereto:

wherein the content of the first and second substances,

In the invention, the 4-hydropyran series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by 4-H pyran aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:

wherein each W is independently selected from

Wherein each V is independently an atom or group having an electron withdrawing effect, preferably from an oxygen atom or a sulfur atom, more preferably from an oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:

wherein Ar is₁、Ar₂Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a monocyclic structure, a polycyclic structure or a condensed ring structure; by way of example, suitable Ar' s₁、Ar₂Selected from, but not limited to:

wherein the content of the first and second substances,

each independently attached to any suitable hydrogen atom, substituent group, and substituted polymer chain that may or may not participate in force activation.

Typical structures of the formulae V-1 to V-3 may be illustrated below, but the invention is not limited thereto:

wherein the content of the first and second substances,

In the present invention, non-covalent single force sensitive groups based on the composition include, but are not limited to, the following series: non-covalent single force sensitive groups based on host-guest compositions, non-covalent single force sensitive groups based on energy transfer compositions.

In the present invention, the non-covalent single force-sensitive group based on a host-guest composition refers to a composition comprising at least one host molecule/group and at least one guest molecule/group, and the host molecule/group and the guest molecule/group form a composition through a host-guest interaction, wherein the host molecule/group and/or the guest molecule/group may or may not have force responsiveness, and at least one of the host molecule/group and the guest molecule/group is covalently linked to a polymer chain; under the action of mechanical force, the host-guest composition is stressed and activated to change the luminescent property, the fluorescence/phosphorescence property and the long afterglow luminescent property, and show specific force-induced response.

The host molecule/group can be exemplified as follows, but the invention is not limited thereto:

the guest molecules/groups can be exemplified as follows, but the invention is not limited thereto:

in the present invention, the non-covalent single force sensitive group based on the energy transfer composition refers to a non-covalent force response element formed by combining a non-mechanical force responsive energy donor and a non-mechanical force responsive energy acceptor which can transfer energy with each other, wherein the energy donor and the energy acceptor are respectively not responded by mechanical force, and when mechanical force is acted, the distance, arrangement form and the like between the energy donor and the energy acceptor are changed, so that the energy transfer process between the energy donor and the energy acceptor is weakened/inhibited or enhanced/promoted, and the fluorescence wavelength shift, fluorescence intensity enhancement or weakening, fluorescence lifetime extension or shortening and the like generated by the change show specific force response.

In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; in another case, when the energy donor emits light, energy transfer to the adjacent energy acceptor is achieved through dipole resonance interaction between the energy donor and the energy acceptor. In order to achieve energy transfer between the energy donor and the energy acceptor to achieve the desired force-induced response effect, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) the energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.

In the present invention, the energy donor in the non-covalent single force sensitive moiety of the energy transfer composition may be selected from non-mechanical force responsive fluorophores and/or luminophores, and the energy acceptor may be selected from non-mechanical force responsive fluorophores and/or quenchers.

In the present invention, the energy donor and the energy acceptor contained in the non-covalent single force sensitive group of the energy transfer composition may be selected from the group consisting of, but not limited to, pre-existing, photo-activated, thermal-activated, electro-activated, chemical-activated, bio-activated, magnetic-activated moieties, and does not include force-activated moieties. In the present invention, when multiple energy donors and multiple energy acceptors are contained in the same polymer, each of the energy donors and energy acceptors can have more than one source. In a preferred embodiment of the present invention, all energy donors and energy acceptors are pre-existing, which facilitates force-induced activation by controlling mechanical force action alone, resulting in rapid and stable force-induced response; in another preferred embodiment of the invention, the part of the energy donor or energy donor is pre-existing, and the other part of the energy donor and energy acceptor is selected from the group consisting of those generated by photoactivation, those generated by thermal activation, those generated by electrical activation, those generated by chemical activation, those generated by biological activation, those generated by magnetic activation, and thus facilitates the achievement of a force-induced response effect by light control, thermal control, electrical control, chemical stimulation, biological stimulation and mechanical force in a dual or multiple coordinated control; in another preferred embodiment of the present invention, the energy donor and the energy acceptor are selected from one or more of photoactivated, thermoactivated, electroactive, chemically activated, biologically activated and magnetically activated, which is advantageous for obtaining abundant non-mechanical force response and achieving multiple coordinated force-induced response effects with mechanical force control of the composition to meet the needs of various special application scenarios.

In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group of the energy transfer composition may be on the same polymer chain, on different polymer chains, or one of them may be on the polymer chain; wherein the energy donor and the energy acceptor can be linked to the polymer chain by covalent and/or supramolecular interactions. In the embodiment of the present invention, it is preferable that the energy donor and the energy acceptor are spaced from each other by not more than 10nm, and it is more preferable that the energy donor and the acceptor are kept close to each other by supramolecular interaction and spaced from each other by not more than 10 nm. The supramolecular action described herein, which may be any suitable supramolecular action, includes but is not limited to: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding, radical cation dimerization, phase separation, crystallization; under the action of mechanical force, the supermolecule action is destroyed, so that the energy transfer process is changed, and force-induced responsiveness is obtained; furthermore, due to the reversible nature of the supramolecular interaction, the force sensitive group may also be given a reversible, recyclable force-responsive effect.

In the invention, the energy transfer can be organically regulated and controlled by designing, selecting and adjusting the type, the quantity and the combination of the energy donor/the energy donor, so that excellent diversified and cooperatively controlled energy transfer performance and wide application are obtained.

In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group based on the energy transfer composition may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.

In the present invention, the energy transfer in the non-covalent single force sensitive groups based on the energy transfer composition may be of only one stage or may be of multiple stages. When the polymer contains a plurality of fluorophores/luminophores (or precursors thereof), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is taken as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, so that the phenomenon of multi-stage energy transfer is realized. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.

In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is shorter than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon that the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregate fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the fluorescence quenching refers to the property that some fluorophores/luminophores are aggregated to generate fluorescence quenching, and the self-quenching phenomenon is generated when the concentration of the fluorophores/luminophores is too large.

In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive, and magnetically activated.

In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from the group consisting of, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.

Among these, the covalent organic fluorophores can be exemplified as follows, but the present invention is not limited thereto:

among them, the following are examples of the aggregation-induced emission organic fluorophore, but the present invention is not limited thereto:

the organic fluorophores of the other non-covalent complexes, self-assemblies, aggregates, compositions and various combinations thereof may be selected from any suitable structure. Wherein the composition organic fluorophore may itself be a donor and acceptor composition having energy transfer properties.

Among them, the organometallic fluorophore may be exemplified as follows, but the present invention is not limited thereto:

among them, the organic element fluorophore may be exemplified as follows, but the present invention is not limited thereto:

among them, the biological fluorophore can be exemplified as follows, but the present invention is not limited thereto:

GFP、EGFP、GFP-S65T、BFP、CFP、YFP、EBFP、Azurite、EBFP2、mTagBFP、TagRFP、EYFP、ECFP、Cerulean、mTFP、mTurquoise、mCitrine、mVenus、CyPet、YPet、phiYFP、DsRed、mBanana、morange、dTomato、mTangerine、mStrawberry、mCherry、mKO、GFP-Phe66、Sirius、mPlum、mKate、mKate2、Katushka、mNeptune、TagRFP657、IFP1.4、T-Sapphire、mAmetrine、mKeima、mLSS-Katel、mLSS-Kate2；

the inorganic fluorophores include but are not limited to sulfide fluorophores, aluminate fluorophores, silicate fluorophores, nitride fluorophores, oxide fluorophores, oxynitride fluorophores, rare earth fluorophores, and inorganic non-metal quantum dots, wherein part of the inorganic fluorophores are mainly composed of a substrate: activator composition, inorganic fluorophores may be exemplified as follows, but the invention is not limited thereto:

CaS：Eu、SrS：Ce、SrGa₂S₄：Eu、SrAl₂O₄：Ce、CaAl₂O₄：Eu、BaAl₂O₄：Ce、Lu₃Al₅O₁₂：Eu、Y₃Al₅O₁₂：Ce、Tb₃Al₅O₁₂：Ce、Gd₃Al₅O₁₂：Eu、Ba₂SiO₄：Eu、Sr₂SiO₄：Eu、BaSi₂O₃：Eu、BaSiO₃：Eu、Ba₃SiO₅：Eu、Ba₂Si₃O₈：Eu、Ba₃Si₅O₁₃：Eu、Ba₉Sc₂Si₆O₂₄：Eu、Ca₃Mg₂Si₃O₁₂：Ce、Ca₃Sc₂Si₃O₁₂：Ce、Ca₂Si₂O₇：Eu、SrLi₂SiO₄：Eu、CaLi₂SiO₄：Eu、Ca₂Si₅N₈：Eu、Sr₂Si₅N₈：Eu、CaAlSiN₃：Eu、ZnO：Eu、ZnO：Li、SrSi₂N₂O₂：Eu、CaSi₂N₂O₂: eu, CdS/ZnS quantum dots, ZnSe/ZnS quantum dots, InP/ZnS quantum dots, CdSe/ZnS quantum dots, carbon quantum dots, PbS quantum dots with emission wavelength in the near infrared region, ZnS: cu series long afterglow material, CaS: bi-series long afterglow material, SrAl₂O₄: eu, Dy series long afterglow material, CaAl₂O₄: eu, Nd series long afterglow material, Sr₄Al₁₄O₂₅: eu, Dy series long afterglow material, Zn₂SiO₄: mn, As series long afterglow material, Sr₂MgSi₂O₇: eu, Dy series long afterglow phosphor, Ca₂MgSi₂O₇: eu, Dy series long afterglow material, MgSiO₃: mn, Eu, Dy series long afterglow material, CaTiO₃: pr, Al series long afterglow material, Ca₈Zn(SiO₄)₄Cl₂: eu series long afterglow phosphor, Ca₂Si₅N₈: eu series long afterglow materials;

inorganic up-converting phosphors typically consist of a host, an activator and a sensitizer, usually doped into nanoparticles or glass by rare earth ions, to absorb long-wavelength radiation and emit short-wavelength fluorescence. Among them, rare earth ions can be exemplified as follows, but the present invention is not limited thereto: scandium ion, yttrium ion, lanthanum ion, cerium ion, neodymium ion, praseodymium ion, promethium ion, europium ion, samarium ion, terbium ion, gadolinium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, lutetium ion, ytterbium ion;

among these, inorganic up-converting fluorophores can be exemplified as follows, but the present invention is not limited thereto:

NaYF₄：Er、CaF₂：Er、Gd₂(MoO₄)₃：Er、Y₂O₃：Er、Gd₂O₂S：Er、BaY₂F₈：Er、LiNbO₃：Er，Yb，Ln、Gd₂O₂：Er，Yb、Y₃Al₅O₁₂：Er，Yb、TiO₂：Er，Yb、YF₃：Er，Yb、Lu₂O₃：Yb，Tm、NaYF₄：Er，Yb、LaCl₃：Pr、NaGdF₄：Yb，Tm@NaGdF₄: core-shell nanostructure of Ln, NaYF₄：Yb，Tm、Y2BaZnO₅：Yb，Ho、NaYF₄：Yb，Er@NaYF₄: core-shell nanostructure of Yb, Tm, NaYF₄：Yb，Tm@NaGdF₄: core-shell nanostructures of Yb.

The organic up-converting fluorophore is preferably an organic composition which achieves up-conversion effect by triplet-triplet annihilation based, said organic composition mainly consisting of a sensitizer and an organic up-converting energy acceptor.

Among them, the following sensitizers can be exemplified, but the present invention is not limited thereto:

among them, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:

in the present invention, fluorophores such as organic fluorophores, organic metal fluorophores, organic element fluorophores, biological fluorophores, organic upconversion fluorophores, inorganic fluorophores, and inorganic upconversion fluorophores can also form various noncovalent complexes, self-assemblies, aggregates, and combinations thereof, which can be the same or different.

In the present invention, the fluorophore generated by chemical activation refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a chemical reaction. Suitable structures that can be chemically activated to generate fluorophores can be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be chemically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the fluorescence generated by biological activation refers to a structure having fluorescence in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed in structure by a biological reaction. Suitable bioactivatable fluorophore generating structures may be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores, although the invention is not limited thereto. The various force-sensitive moieties/groups of the invention having force-sensitive properties can also be biologically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the photo-activation generated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a photoreaction. Suitable photoactivatable fluorophore-generating structures can be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores. The following may be exemplified, but the invention is not limited thereto:

PA-GFP (trademark), PA-mCherry1 (trademark), Kaede (trademark), PS-CFP2 (trademark), mEosFP (trademark), Dendra2 (trademark), Dronpa (trademark), rsFasLime (trademark), Pandon (trademark), bsDronpa (trademark), Kindling (trademark).

The force-sensitive moieties/groups of the present invention having force-sensitive properties can also be photoactivated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the thermally activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor of the fluorophore is changed by a structural change due to a thermal reaction. Suitable structures for the heat-activatable fluorophores can be obtained by suitable structural modification and derivatization of the suitable fluorophores mentioned above, but the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be thermally activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the electrically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by structural change of its precursor under the action of an electric stress is changed. Suitable structures that can be electroactive to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be electroactive under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the magnetically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a magnetic reaction. Suitable structures which can be magnetically activated to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be magnetically activated under suitable conditions without a force-sensitive response to generate a fluorophore.

In the present invention, the fluorophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable fluorescent moiety and a quencher moiety, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to generate fluorescence from the fluorescent moiety, which may be any suitable entity as described above that can generate fluorescence upon excitation with light of a suitable wavelength.

In the present invention, the fluorophore may function as an energy donor under suitable conditions and may function as an energy acceptor under otherwise suitable conditions. By rational utilization of the fluorophores, a desirable combination of energy donors and acceptors can be obtained, resulting in excellent energy transfer properties.

In the present invention, the luminophore may be selected from, but not limited to, chemical activation generated, biological activation generated, photoactivation generated/photoluminescent, thermoactivation generated/thermoluminescable, electroactive generated/electroluminescent, magnetic activation generated/magnetoluminesceable.

In the present invention, the precursor of the luminophore generated by the chemical activation is called a chemiluminescent group, which refers to a chemical group capable of generating a luminescence phenomenon by a structural change after a chemical reaction, and includes, but is not limited to, a suitable dioxetane chemiluminescent system, a luminol chemiluminescent system, an oxalate peroxide chemiluminescent system, an acidic potassium permanganate chemiluminescent system, a tetravalent cerium chemiluminescent system, an acridinium ester chemiluminescent system, and a fluorescein chemiluminescent system.

Wherein the suitable dioxetane chemiluminescent system is comprised of a suitable dioxetane compound and a fluorescer, wherein the suitable dioxetane compound may be exemplified by, but is not limited to:

among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:

5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;

the luminol chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:

the oxalate peroxide chemiluminescence system comprises an oxalate compound, a fluorescent agent and hydrogen peroxide, wherein the oxalate compound can be exemplified as follows, but the invention is not limited to the following:

the chemiluminescence system of the acidic potassium permanganate consists of acidic potassium permanganate and a substance to be detected, and some adaptive compounds can be added to enhance the chemiluminescence intensity of the acidic potassium permanganate₄Test substance or acidic KMnO₄- (luminescence enhancer) -analyte, which may be exemplified as follows, but the present invention is not limited thereto:

acidic KMnO₄Oxalate, acidic KMnO₄Luminol, acidic KMnO₄- (divalent lead ion) -luminol, acidic KMnO₄-SO₂Acidic KMnO₄Sulfite, acidic KMnO₄Glutamic acid, acidic KMnO₄Aspartic acid, acidic KMnO₄- (Formaldehyde) -L-Tryptophan, acidic KMnO₄- (Formaldehyde) -methotrexate, acidic KMnO₄- (Formaldehyde) -Dichloromethabenzuron, acidic KMnO₄- (Formaldehyde) -Aminopyrine, acidic KMnO₄- (Formaldehyde) -iodine, acidic KMnO₄- (Formaldehyde) -tyrosine, acidic KMnO₄- (glyoxal) -imipramine, acidic KMnO₄- (glyoxal) -dipyridamole, acidic KMnO₄- (glyoxal) -reserpine, acidic KMnO₄- (sodium dithionite) -riboflavin, acidic KMnO₄- (sodium dithionite) -tetrahydropalmatine, acidic KMnO₄- (Ling)Sodium disulfite) -vitamin B₆Acidic KMnO₄- (sodium dithionite) -pipemidic acid, acidic KMnO₄Morphine, acidic KMnO₄-buprenorphine, acidic KMnO₄-para-aminobenzoate, acidic KMnO₄Codeine, acidic KMnO₄Tryptophan, acidic KMnO₄Dopamine, acidic KMnO₄Levodopa, acidic KMnO₄Adrenaline, acidic KMnO₄-methoxybenzylaminopyridine, acidic KMnO₄-DL-malic acid;

the tetravalent cerium chemiluminescence system is composed of tetravalent cerium and a test object, and some adaptive compounds can be added to enhance the chemiluminescence intensity, and in the invention, the tetravalent cerium chemiluminescence system is expressed as a tetravalent cerium-test object or a tetravalent cerium- (luminescence enhancer) -test object, which can be exemplified as follows, but the invention is not limited thereto:

tetravalent cerium-paracetamol, tetravalent cerium-naproxen, tetravalent cerium-phenacetin, tetravalent cerium-biphenyltriphenol, tetravalent cerium-sulfite, tetravalent cerium- (quinine) -penicillamine, tetravalent cerium- (quinine) -2-mercaptoethane sulfonate, tetravalent cerium- (quinine) -cysteine, tetravalent cerium- (quinine) -thiazole Schiff base, tetravalent cerium- (quinine) -sulfite, tetravalent cerium- (cinchonine) -sulfite, tetravalent cerium- (ciprofloxacin) -sulfite, tetravalent cerium- (oxfloxacin) -sulfite, tetravalent cerium- (norfloxacin) -sulfite, pentavalent cerium-and-bismuth-containing compound, and mixtures thereof, Tetravalent cerium- (sipafloxacin) -sulfite, tetravalent cerium- (roxofloxacin) -sulfite, tetravalent cerium- (Luofloxacin) -sulfite, (IV), (V) and (V)

+ enoxacin-sulfite, tetravalent cerium- (E)

+ fleroxacin) -sulfite, tetravalent cerium-, (four valence

+ gatifloxacin-sulfite, tetravalent cerium- (N-tetrahydrobenzothiazole imine Schiff base) -sulfite,Tetravalent cerium-rhodamine 5G, tetravalent cerium- (rhodamine B) -folic acid, tetravalent cerium- (rhodamine B) -ascorbic acid;

among them, the acridinium ester chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:

4- (2-succinimidylcarbonyl) phenyl-10-methylacridine-9-carboxylate fluorosulfonate;

the fluorescein chemiluminescence system can be exemplified as follows, but the invention is not limited to the following:

in the present invention, the biologically-activated luminophore, a precursor thereof, is referred to as a biologically-activatable luminophore, which refers to a chemical or biological group that is capable of undergoing a structural change by a biological reaction (e.g., catalysis by a biological enzyme) to produce a luminescence phenomenon. The bioactivated luminescence may be exemplified as follows, but the present invention is not limited thereto: marine animal luminescence, bacterial luminescence, firefly luminescence; wherein the marine animals are luminous, including but not limited to luminous marine animals such as noctiluca, dinoflagellate, radioworms, jellyfish, sea feathers, ctenopharyngodon idellus, multicastoma, krill, cerasus, cephalopods, echinoderm, tunicates, fish, clamworm, sea bamboo shoot, sea worm, copepods, schizothorax, Phillips longifolus, columna gigas and the like; the bacteria emit light, and the bacteria include but are not limited to luminescent heterobrevibacterium, luminous bacillus leiognathi, Shewanella villosa, alteromonas haiensis, Vibrio harveyi, Vibrio livialis biotype I, Vibrio fischeri, Vibrio paradoxus, Vibrio orientalis, Vibrio mediterranei, Vibrio arctica, Vibrio cholerae, Vibrio qinghai and the like; the firefly luminescence includes but is not limited to fluorescein bioluminescence and dioxetane bioluminescence.

In the present invention, the photo-activation generated/photo-luminescent luminophore and its precursor are called photo-activation luminophores, which refer to chemical groups that can undergo a structural change after a photo-reaction, thereby generating a luminescence phenomenon.

In the present invention, the thermally activated/thermoluminescable luminophore precursor thereof is referred to as a thermoactivatable luminophore, which refers to a chemical group that is capable of undergoing a structural change upon thermal reaction, thereby generating a luminescence phenomenon.

In the present invention, the electroactive produced/electroluminescent luminophore and its precursor are referred to as an electroactive luminophore, which means a chemical group that can generate a luminescence phenomenon by a structural change or charge/hole combination or electrical excitation after an electrochemical reaction. Examples thereof may be as follows, but the present invention is not limited thereto:

in the present invention, the electrically activatable luminophores further comprise organic light emitting diodes and inorganic light emitting diodes. Wherein, the organic light emitting diode includes, but not limited to, an organic small molecule light emitting diode and an organic polymer light emitting diode; wherein the electron transport layer material in the organic small molecule light emitting diode can be selected from fluorescent dye compounds such as Alq, Znq, Gaq, Bebq, Balq, DPVBi, ZnSPB, PBD, OXD, BBOT, etc.; the material of the hole transport layer is selected from, but not limited to, aromatic amine fluorescent compounds, such as organic materials like TPD, TDATA, etc. Organic polymer light emitting diodes include, but are not limited to: organic electroluminescent materials such as poly (p-phenylenes), poly (acetylenes), poly (carbazoles), polyfluorenes, and polythiophenes. Wherein, the inorganic light emitting diode material includes but not limited to: gallium arsenide light emitting diodes, gallium phosphide light emitting diodes, silicon carbide light emitting diodes, gallium nitride light emitting diodes, zinc selenide light emitting diodes, gallium phosphide light emitting diodes, aluminum arsenide light emitting diodes.

In the present invention, the magnetically activated/magnetoluminesceable luminophore and its precursor are referred to as magnetically activated luminophores, which refer to chemical groups capable of undergoing a structural change after a magnetic reaction, thereby generating a luminescence phenomenon.

In the present invention, the luminophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable luminophore and a quencher, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to produce luminescence from the luminophore, which may be any suitable entity as described above that can produce luminescence upon excitation with light of a suitable wavelength.

It is noted that the same luminophore can exist simultaneously with one or more activated luminescence processes, such as dioxetane luminescence, oxalate peroxide luminescence, fluorescein luminescence, both chemically activated luminescence and biologically activated luminescence.

In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated. Groups that can act as pre-existing quencher energy acceptors include, but are not limited to: quenching dyes having a basic skeleton such as NPI, NBD, DABCYL, BHQ, ATTO, Eclipse, MGB, QXL, QSY, Cy, Lowa Black, and IRDYE, and quenching dye derivatives thereof include, specifically, the following:

ATT0540Q (trade name), ATT0580Q (trade name), ATT0612Q (trade name), Eclipse (trade name), MGB (trade name), QXL490 (trade name), QXL520 (trade name), QXL570 (trade name), QXL610 (trade name), QXL670 (trade name), QXL680 (trade name), Cy5Q (trade name), Cy7Q (trade name), Lowa Black FQ (trade name), Lowa Black RQ (trade name), IRDYE QC-1 (trade name).

In the present invention, the fluorophore having an aggregate fluorescence quenching property includes, but is not limited to, triphenylamine-based fluorophore, fused ring-based fluorophore, rylimide-based fluorophore, rubrene-based fluorophore, porphyrin-based fluorophore, phthalocyanine-based fluorophore, and the like, and specifically, the following may be cited:

in the invention, the quenching group can also be selected from a structure with fluorescence quenching performance generated by activating a part of force-sensitive elements/force-sensitive groups with force-sensitive characteristics under other actions besides the mechanical force action.

In the present invention, suitable activatable fluorophores, luminophores, quenchers, which may have two or more activation methods, may be used independently, simultaneously or sequentially, and the different activation methods may even produce different activation effects.

In the present invention, the force-sensitive moiety/group having force-sensitive property capable of generating a fluorophore and/or a quencher by an activation action of one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc. other than mechanical force is mainly selected from a radical type structure, a five-membered ring structure, a six-membered ring structure, a cyclobutane structure, a monoacyclocyclobutane structure, a dioxetane structure, a cyclobutene structure, a DA structure, a hetero DA structure, a light-operated DA structure, a [4+4] cycloaddition structure, a metal-ligand structure. The force-sensitive element/group with force-sensitive property capable of generating a luminophore by other than mechanical force, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc., is selected from dioxetane structures. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.

In the present invention, in order to obtain the desired force-responsive properties, the non-covalent single force-sensitive groups of the energy transfer-based composition must be aligned in a suitable manner, preferably with nearly parallel transfer dipole orientation, in addition to satisfying the partial overlap of the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor and the need for sufficient proximity of the energy donor and the energy acceptor.

The composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and comprises but is not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-component composite structure formed by multi-component combination of the tying, gating, parallel and serial structures and the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.

In the present invention, the tethered complex force-sensitive moiety is formed by any suitable one of the above-mentioned covalent or non-covalent force-sensitive moiety/single force-sensitive moiety modules being bound to any suitable linker or linkers, wherein the force-sensitive moiety/single force-sensitive moiety module is tethered by the linker, and after the force-sensitive moiety/single force-sensitive moiety is activated, the tethered linker can prevent (at least temporarily) the polymer chain from chain scission due to chain scission caused by the activation of the chain scission type force-sensitive moiety/single force-sensitive moiety or the activated non-chain scission type force-sensitive moiety/single force-sensitive moiety from continuing to be stressed to cause chain scission. The complex force sensitive groups of the tethered structure are particularly useful for preventing, at least temporarily, or slowing down the chain scission of the polymer chains due to activation of the force sensitive groups, which is extremely important for both achieving force-responsive responsiveness and protecting the polymer from chain scission damage. A typical tethering force sensitive moiety has the general structural formula shown below, but the invention is not limited thereto.

Wherein the content of the first and second substances,

is force sensitive element/single force sensitive group;

is a linker, which may be selected from small molecule and large molecule linkers;

is a link to any suitable polymer chain/group/atom.

In the present invention, the tethering linker may be formed by at least one of a common covalent bond, a dynamic covalent bond, and a supramolecular interaction. The force-sensitive module can be composed of chain-breaking type covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, chain-breaking type non-dynamic covalent force-sensitive element/single force-sensitive group, chain-breaking type non-covalent force-sensitive element/single force-sensitive group. When the force-sensitive module is a chain-breaking non-dynamic covalent force-sensitive element/single force-sensitive group and the tethered connecting group is formed by common covalent bonds, the tethered structure is a non-dynamic non-chain-breaking tethered composite force-sensitive group. When only the force-sensitive module has dynamic covalent or non-covalent characteristics, and the tethered linker is formed by a common covalent bond, the tethered structure is a dynamic non-delinking tethered complex force-sensitive group. When the force-sensitive module has dynamic covalent character or non-covalent character and the tethering connection group is formed by dynamic covalent bond and/or supermolecular action, the tethering structure is a dynamic chain-breaking tethering composite force-sensitive group. When the force-sensitive module is a delinking non-dynamic covalent force-sensitive motif/single force-sensitive group and the tethered linker is formed by dynamic covalent bonds and/or supramolecular interactions, the tethered structure is a partially dynamic delinking tethered complex force-sensitive group. When the tethered linker is formed by only ordinary covalent bonds, the tethered linker is the most stable in structure and is most able to withstand complete chain scission of the polymer chain following activation by the tethered force-sensitive moiety/single force-sensitive group. Regardless of whether the force-sensitive module is dynamic or not, once the tethering linker contains dynamic covalent bonds and/or supramolecular interactions, the performance of the dynamic covalent bonds and/or supramolecular interactions can be realized by the dynamic covalent bonds and/or supramolecular interactions after final activation, and the force-sensitive module is dynamic.

In embodiments of the invention, the tethered complex force-sensitive groups preferably tether split homolytic, heterolytic, retrocyclic and non-covalent force-sensitive moieties/single force-sensitive groups of the split-chain type.

In an embodiment of the invention, the homolytic force sensing element/single force sensing group used for tethering is preferably a reversible free radical structure in the bis/polysulfide series, bis/polyselenium series, bis-aryl furanone series, bis-aryl cyclic ketone series, bis-aryl cyclopentenone series, bis-aryl chromene series, aryl biimidazole series, aryl ethane series, dicyano tetraaryl ethane series, aryl pinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane substituted ethane series, bifluorene series, allyl sulfide series, thio/seleno ester series.

In embodiments of the invention, the heterolytic mechanism force sensitive element/single force sensitive group used for tethering is preferably a structure in the triarylsulfonium salt series.

In an embodiment of the invention, the reverse cyclization mechanism force-sensitive moiety/single force-sensitive group used for tethering is preferably a structure in the cyclobutane series, dioxetane series, DA series, heteroda series, [4+4] cycloaddition series.

In an embodiment of the invention, the non-covalent force-sensitive motif/single force-sensitive group used for tethering is preferably a platinum alkyne ligand, an azacarbene with silver/copper/gold/ruthenium ligand, a boron nitrogen ligand, a palladium phosphorus ligand, a ruthenium ligand, a ferrocene, a cobaltocene.

In the embodiment of the present invention, the linking group for tethering is preferably a hydrocarbon group, a hydrocarbon group containing a heteroatom, a polyester group, a polyethylene glycol group.

In the embodiment of the present invention, some preferred tethered complex force-sensitive groups have the following general structural formula, but the present invention is not limited thereto.

Wherein the content of the first and second substances,

selected from:

wherein the content of the first and second substances,

selected from:

wherein the content of the first and second substances,

to be connected with n

An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, a fused ring structure, a bridged ring structure, and a nested ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphine atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions

Are the same or different; unless otherwise indicated, appear hereinafter

The same meanings are given, and description thereof will not be repeated; wherein the content of the first and second substances,

is a link to any suitable polymer chain/group/atom;

is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n is

The number of the cells.

In the embodiments of the present invention, some preferred tethered complex force-sensitive groups are exemplified below, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.

Wherein the content of the first and second substances,

is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is selected from the group consisting of but not limited toHydrogen atom, hydrocarbyl.

In the present invention, the gated complex force sensitive moiety, which is formed by binding any suitable two or more covalent or non-covalent force sensitive motif/single force sensitive moiety modules, can be sequentially activated, and only the module which is used as a substrate can be activated after the module which is used as the gated module is activated. In gated complex force sensors with only two modules combined, one module is gated and the other is gated as substrate. In a gated complex force sensor comprising three modules, one of the modules is gated by both a preceding and a subsequent activation module. When four or more modules are contained in the gated complex force-sensitive cluster, and n represents the total number of modules, the number of modules which are both substrates of the preceding activation module and gated of the subsequent activation module is n-2. When the activation force of the gate control module is higher than that of the substrate module, once the gate control module is activated by force, the substrate module is immediately activated, on one hand, the gate control module protects the substrate module, on the other hand, the gate control module indirectly improves the activation force of the substrate module, the substrate module is favorable for the substrate module to play a role under the action of higher external force on a polymer, and the functional significance of stress warning and the like is particularly outstanding. When the activation force of the gating module is lower than that of the substrate module, the substrate is not activated immediately after gating activation, and the substrate must be activated after the external force rises to reach the threshold of the activation force; on one hand, sequential force-induced responses can be obtained through stepwise activation, and different responses can give different effects, such as stress warning and the like; on the other hand, when a polymer chain contains a plurality of the gated complex force-sensitive groups, activation of the substrate is started only after activation of all the activatable gates, so that stepwise multiple activation is generated, which is beneficial to protect the polymer and improve the toughness of the polymer in multiple layers besides sequential force-induced response. When the activation force of the gating module is equal to that of the substrate module, the substrate is rapidly activated after gating activation, although gating cannot effectively protect the substrate and cannot generate step-type activation, sequential activation of a plurality of modules can generate multiple identical or different force-induced responses, and the method also has a positive effect on improving the toughness of the polymer. A typical gated complex force-sensitive moiety has a general structural formula as shown in the following formula, but the present invention is not limited thereto.

Wherein the content of the first and second substances,

is a force sensitive element/single force sensitive group, and p is the number of modules which are not only substrates of a preceding activation module but also gates of a following activation module;

is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different;

is a link to any suitable polymer chain/group/atom.

In the present invention, the gating module may be selected from the group consisting of a chain-broken type and a non-chain-broken type. The substrate module may also be of the delicatessen or non-delicatessen type. Regardless of whether the gating module and the substrate module are of the broken-chain type, it must be ensured that the gating module is activated prior to the substrate module being subjected to force. The chain-breaking gating module comprises chain-breaking covalent force-sensitive elements/single force-sensitive groups with dynamic covalent characteristics, chain-breaking non-dynamic covalent force-sensitive elements/single force-sensitive groups and chain-breaking non-covalent force-sensitive elements/single force-sensitive groups. When the gating module and the substrate module are both selected from any one of a chain-breaking covalent force-sensitive element/single force-sensitive group and a chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the gating composite force-sensitive group has complete dynamic; however, if only one module is selected from any one of the chain-breaking covalent force-sensitive element/single force-sensitive group and the chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent character, the gated composite force-sensitive group has only partial dynamic property.

In the present invention, the linking group in the gated composite force sensitive group can be selected from small molecule or large molecule linking groups formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein the linker formed by the common covalent bond facilitates force activation of the substrate module. A linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.

In an embodiment of the present invention, the preferred gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain-breaking type, including but not limited to homolytic, heterolytic, reverse cyclic, and non-covalent force-sensitive element/single force-sensitive group; the substrate force-sensitive moiety/monodispersion may be any suitable force-sensitive moiety/monodispersion, preferably homolytic, heterolytic, reverse cyclization, electrocyclization, bending activation and non-covalent force-sensitive moiety/monodispersion.

In embodiments of the present invention, preferred gating moieties/groups include, but are not limited to, disulfide bonds, diselenide bonds, diarylfuranone groups, diarylcycloketo groups, diarylcyclopentenedione groups, diarylchromone groups, arylbiimidazolyl groups, arylethyl groups, dicyanotetraarylethyl groups, arylpinacol groups, alkoxyamino groups, alkylthioamino groups, cyclohexadienone groups, tetracyanoethyl groups, cyanoacylethyl groups, adamantane-substituted ethyl groups, dibenzoenyl groups, allylthioether groups, thioester groups, selenoate groups, cyclobutane groups, dioxethyl groups, DA cyclic groups, hetero DA cyclic groups, [4+4] cyclic groups, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocene, cobaltocene.

In embodiments of the present invention, preferred substrate motifs/groups include, but are not limited to, disulfide bonds, bisseleno bonds, bisarylfuranones, bisarylcycloketones, bisarylcyclopentenediones, bisarylene-based, arylbiimidazoles, arylethanes, dicyanotetraarylethanes, arylpinacols, alkoxyamines, alkylthioamines, cyclohexadienones, tetracyanoethanes, cyanoacylethanes, adamantane-substituted ethanes, bifluorenes, allylthioether groups, thioesters, selenoates, cyclobutanes, dioxetanes, DA cyclics, hetero DA cyclics, [4+4] cyclics, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocenes, cobaltocenes, six-membered rings, five-membered rings, Cyclopropane, oxirane.

Some preferred gated complex force sensors are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.

Wherein the content of the first and second substances,

is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r₁Is hydrogen, hydroxy, a protecting group, R₂Is hydrogen, halogen, R₃Hydrogen, a fluorophore.

In the present invention, a parallel composite force-sensitive cluster is formed by combining any suitable two or more suitable force-sensitive elementary/single force-sensitive cluster modules in a parallel connection manner, wherein all the force-sensitive elementary/single force-sensitive cluster modules can be stressed simultaneously. Wherein, the parallel force-sensitive elements/single force-sensitive mass modules can be the same or different; when the same, the activation force required by one parallel complex force-sensitive cluster is equivalent to the activation force required by two or more single force-sensitive clusters, and each force-sensitive element/single force-sensitive cluster module will typically be activated simultaneously; when not identical, different force-sensitive elements/single force-sensitive mass modules may not activate simultaneously if the activation force is different for each force-sensitive mass. A typical parallel complex force-sensitive group has a general structural formula shown in the following formula, but the invention is not limited thereto.

Wherein the content of the first and second substances,

the force-sensitive elements/single force-sensitive groups are arranged, m is the number of the force-sensitive elements/single force-sensitive groups connected in parallel, and the force-sensitive elements/single force-sensitive groups at different positions can be the same or different; r, R,

The linking group can be selected from small molecule linking groups and large molecule linking groups, and the linking groups at different positions can be the same or different;

is a link to any suitable polymer chain/group/atom.

In the invention, the force-sensitive modules in the parallel composite force-sensitive clusters can be selected from a chain-breaking type and a non-chain-breaking type. When any one force sensitive module is in a dynamic chain-breaking structure, the dynamic property is conveniently provided. When all the parallel force-sensitive modules are selected from covalent force-sensitive group elements/single force-sensitive groups and non-covalent force-sensitive group elements/single force-sensitive groups with dynamic covalent characteristics, the parallel composite force-sensitive groups are dynamic chain-breaking composite force-sensitive groups. When any one force-sensitive module is a non-dynamic covalent force-sensitive element/single force-sensitive group and the connecting group is a common covalent bond structure, the parallel composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.

In the present invention, the linking group in the parallel composite force sensitive group can be selected from small molecule or large molecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein, the connecting base formed by common covalent bond is convenient for the force activation of the force sensitive module; a linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.

Some preferred parallel complex force-sensitive clusters are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.

Wherein the content of the first and second substances,

for attachment to any suitable polymer chain/group/atom, attachment to the polymer chain is preferably via an ether linkage, an ester group, a phenoxy group, an amide linkage, a urethane linkage, a tertiary amine group, a triazole group, a double bond. In the present invention, the activation force required by the parallel force sensing mass is the sum of the individual parallel units, but not the sum effect when the individual units are not activated simultaneously. The parallel force sensitive groups provide richer performance and selection for the force-induced response of the material, and particularly the comprehensive mechanical strength of the force sensitive groups can be improved.

In the invention, the tandem composite force-sensitive cluster is formed by combining any suitable two or more force-sensitive cells/single force-sensitive cluster modules in a tandem connection manner, the tandem connection group between any two adjacent force-sensitive cells/single force-sensitive cluster modules is part of any one of the two adjacent tandem force-sensitive cells/single force-sensitive cluster modules, and is an indispensable part for realizing force responsiveness/effect of any one of the tandem force-sensitive cells/single force-sensitive cluster modules, and each tandem force-sensitive cell/single force-sensitive cluster module can be activated under the action of a suitable mechanical force. A typical tandem complex force-sensitive group has a general structural formula shown in the following formula, but the present invention is not limited thereto.

Wherein the content of the first and second substances,

the force-sensitive elements/single force-sensitive groups at different positions can be the same or different; r, L is a linking group, which may be selected from a small groupA daughter and a macromolecular linker, the linkers at different positions may be the same or different; n and m are the number of the force sensitive elements/single force sensitive groups connected in series;

is a link to any suitable polymer chain/group/atom.

In the present invention, the force-sensitive modules in the series-connected composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the tandem composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the series-connection composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.

In the invention, the linking group in the tandem composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.

In the embodiment of the invention, the force sensitive element/single force sensitive group in the series composite force sensitive group is a non-chain-breaking module, preferably formed by combining a six-membered ring unit and a five-membered ring unit. Some preferred tandem composite force-sensitive groups are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.

Wherein the content of the first and second substances,

is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r₁、R₂Are any suitable groups/atoms, preferably hydrocarbon groups and hydrogen atoms. The series composite force sensitive group based on the six-membered ring and the five-membered ring is particularly suitable for obtaining multi-level force-induced color change/fluorescence response, can induce different stress effects and obtain synergistic effect through multi-level color change and mixed color/fluorescence, and has important significance for obtaining multifunctional force-induced response.

In the present invention, any one or more of the tethered, gated, parallel, and tandem modules can also be recombined with any suitable one or more force-sensitive motifs and/or single force-sensitive groups and/or linker modules, or any suitable two or more of the tethered, gated, parallel, and tandem modules, to obtain a multiplex composite force-sensitive group. For example, a gated multi-element force sensor group is obtained by tethering a gated composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the tethered composite force sensor group and a single force sensor group module, a multi-level gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the single force sensor group module, two or more series composite force sensor groups are combined into a parallel multi-element composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the series composite force sensor group and the tethered composite force sensor group, a gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the series composite force sensor group, a series multi-element force sensor group is obtained by combining the parallel composite force sensor group and the series composite force sensor group, and a multi-element force sensor group is obtained by continuously tethering the series multi-element force sensor group, and the like. The technical personnel in the field can carry out reasonable combination according to the guidance of the invention to prepare the multielement composite force sensitive groups with various structures and excellent performance. Some exemplary multi-element force-sensitive compound structures are shown below, but the invention is not limited thereto.

Wherein the content of the first and second substances,

the force-sensitive elements/single force-sensitive groups at different positions can be the same or different;

is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n, m and q are the number of the force sensitive elements/single force sensitive groups/compound force sensitive groups/multi-element compound force sensitive groups connected in series/in parallel, and p is the number of gated modules which are not only substrates of the preceding activation modules but also the subsequent activation modules;

is a link to any suitable polymer chain/group/atom.

In the present invention, the force-sensitive modules in the multicomponent composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the multi-element composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the multi-element composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group which has certain dynamic property and is convenient to provide the dynamic property.

In the invention, the linking group in the multi-element composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.

In the invention, the dynamic chain-breaking type multi-component composite force sensitive group must meet the characteristics of dynamic and chain-breaking, and the non-dynamic chain-breaking type multi-component composite force sensitive group only needs to not meet one of the characteristics of dynamic or chain-breaking.

In the embodiment of the present invention, in the multi-element composite force-sensitive group, preferably, the tethered composite force-sensitive element/single force-sensitive group is of a chain-broken type, including but not limited to homolytic, heterolytic, and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain breaking type, including but not limited to homolytic, heterolytic and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the force-sensitive element/single force-sensitive group in the series-connection composite force-sensitive group is a non-chain-breaking module. Some preferred multi-element force-sensitive compounds are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.

Wherein the content of the first and second substances,

is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is any suitable group/atom, preferably a hydrocarbyl group, a methoxy group and an ester group; r₁Is hydrogen, hydroxy, a protecting group, R₂Is hydrogen, halogen, R₃Hydrogen, a fluorophore. The multi-element composite force-sensitive group is beneficial to obtaining multi-level/multiple responses through one force-sensitive group by fusing multi-element/multi-level composite/single force-sensitive group/force-sensitive elements, and maximally utilizes force-induced responses.

In the present invention, energy transfer, in particular force-energy transfer, is also concerned.

In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; alternatively, when the emission from the energy donor comprises mechanoluminescence, energy transfer to the adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor. Wherein, the energy donor can be selected from a fluorophore and/or a luminophore, and the energy acceptor can be selected from a fluorophore and/or a quencher. In order to achieve energy transfer, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) the energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.

In the present invention, at least one energy donor and/or at least one energy acceptor among the energy donors and energy acceptors for the energy transfer by force are directly and/or indirectly generated by the force-sensitive groups on the polymer chain and/or the force-sensitive components/components in the polymerization under force activation. In addition to at least one energy donor or acceptor being generated directly and/or indirectly by force-sensitive groups/components activated by force, one and the same polymer system may also contain one or more other donors and/or acceptors of non-force-inducing origin. That is, the combination of the energy donor and the energy acceptor in which the force-induced energy transfer is generated may include, but is not limited to, the following cases: the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated directly by force and the energy acceptor generated directly by force, the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated indirectly by force and the energy acceptor generated directly by force, the energy donor generated indirectly by other non-force and the energy acceptor generated directly by force, and the energy donor generated indirectly by force and the energy acceptor generated indirectly by force. Furthermore, the present invention does not exclude that activation of a suitable force sensitive moiety under suitable conditions may generate both an energy donor or an energy acceptor, directly and indirectly, or both. Moreover, when multiple energy donors and multiple energy acceptors are contained in the same polymer, more than one source of each energy donor and energy acceptor may be present. Wherein said other non-force-inducing source means that said energy donor/energy acceptor may be directly and/or indirectly generated in addition to said force-inducing activation, including but not limited to pre-existing, photo-activated, thermo-activated, electro-activated, chemically activated, bio-activated, magnetically activated; wherein other activation means may also generate the energy donor/energy acceptor directly and/or indirectly. Furthermore, in embodiments of the present invention, in addition to force-induced energy transfer, other forms of energy transfer may occur in the polymer, i.e., energy transfer between energy donors of other non-force-induced sources and energy acceptors of other sources.

In embodiments of the present invention, it is preferred that the energy donor and the energy acceptor generated directly by force-activated force-sensitive groups are outside the polymer chain, and the energy donor and the energy acceptor generated indirectly by force-activated force-sensitive groups/force-sensitive components/components and other non-force-induced sources may or may not be on the polymer chain, preferably on the polymer chain; preferably the distance between the energy donor and the energy acceptor is not more than 10nm, further preferably on the same polymer chain, even further preferably on the same polymer chain and the distance is not more than 10 nm; preferably, the energy donor and the energy acceptor are separated by no more than 20 atoms, more preferably no more than 10 atoms, and even more preferably no more than 5 atoms. The energy acceptor and donor may be linked covalently and/or non-covalently when they are on the same polymer chain. The non-covalent interaction for linking described herein may be any suitable non-covalent interaction including, but not limited to: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding, radical cation dimerization, phase separation, crystallization; under the action of mechanical force, the non-covalent action is destroyed, so that the energy transfer process is changed, and force-induced responsiveness is obtained; furthermore, due to the reversible nature of the non-covalent interaction, a reversible, recyclable force-responsive effect may also be imparted to the force-sensitive groups. In the invention, the energy transfer including the energy transfer caused by force can be organically regulated and controlled by designing, selecting and regulating the type, the quantity, the combination, the connection mode and the like of the energy donor/energy donor from other non-force-caused sources, so that excellent and diversified energy transfer performance and wide application can be obtained.

In the present invention, the energy donor and the energy acceptor may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.

In the present invention, the energy transfer may be only one stage or may be multi-stage. When the energy transfer polymer contains a plurality of fluorophores/luminophores (precursors), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is used as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, thereby realizing the phenomenon of multi-stage energy transfer. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.

In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is shorter than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon in which the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregation-induced fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the aggregation-induced fluorescence quenching refers to the self-quenching phenomenon that some fluorophores/luminophores have the aggregation-induced fluorescence quenching property and are generated when the concentration of the fluorophores/luminophores is too large.

In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, force-activated generated, chemical activation generated, biological activation generated, photo-activated generated, thermal activation generated, electro-activated generated, magnetic activation generated.

In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.

In the present invention, the force-activated generated fluorophore refers to an entity having fluorescence, in which the excitation wavelength and/or emission wavelength of fluorescence generated by the precursor of the fluorophore is changed by the direct and/or indirect structural change of the precursor under the action of mechanical force, and the precursor of the fluorophore can be referred to as a fluorescence force-sensitive group. The fluorescent force sensitive moiety may or may not fluoresce prior to force activation, but may fluoresce after activation. Wherein, the fluorescence force-sensitive group contains force-sensitive elements, and the force-sensitive elements include but are not limited to covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions and aggregates.

In the invention, the fluorescence force sensitive group/force sensitive component/component comprises a fluorescence single force sensitive group and a fluorescence composite force sensitive group. Wherein the fluorescent single force sensitive group comprises only one force sensitive moiety or only one force sensitive moiety in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-induced response signal, comprising a covalent fluorescent single force sensitive group and a non-covalent fluorescent single force sensitive group. Wherein, the fluorescence composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent fluorescence force-sensitive elements/single force-sensitive groups (including combining with non-fluorescence force-sensitive elements/single force-sensitive groups), and the fluorescence composite force-sensitive group comprises but not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-composite structure formed by multi-stage combination of the two or more of the tying, gating, parallel and serial structures and the fluorescence and/or non-fluorescence force-sensitive elements/single force-sensitive groups. The fluorescent complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.

One or more components of the upconversion fluorophore can be generated directly and/or indirectly through force-induced activation.

In the invention, the organic up-conversion sensitizer can be pre-existing, or can be directly and/or indirectly formed after activation, including but not limited to force activation, biological activation, chemical activation, and photoactivation, and under the action of the organic up-conversion sensitizer directly and/or indirectly formed after activation and an energy receptor, the effect of energy up-conversion is realized, the process of energy up-conversion can be more easily regulated, controlled and designed, and the effect of energy up-conversion is enriched.

In the present invention, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:

in the invention, the organic up-conversion energy receptor can be pre-existing, or can be directly and/or indirectly formed after activation, including but not limited to force activation, biological activation, chemical activation, light activation, thermal activation, magnetic activation, and electric activation, and the organic up-conversion energy receptor directly and/or indirectly formed after activation is under the action of a sensitizer, so that the effect of energy up-conversion is realized, the process of energy up-conversion can be more easily regulated and designed, and the effect of energy up-conversion is enriched.

In the present invention, the luminophore may be selected from, but not limited to, force-activated, chemical-activated, photo-activated/photo-luminescent, thermal-activated/thermoluminescent, electro-activated/electroluminescent, magnetic-activated/magnetoluminescent.

In the present invention, the solid structure capable of force-activated to generate luminophore is called luminous force sensitive group/force sensitive component/component, which refers to a force sensitive group capable of undergoing a structural change directly and/or indirectly under the action of mechanical force to generate a luminescence phenomenon, and includes, but is not limited to, dioxetane-based luminescence single force sensitive groups and composite force sensitive groups.

In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated.

In the present invention, the various pre-existing fluorophores, luminophores, quenchers can also be modified or derivatized as appropriate to generate structural precursors that can be activated by non-force-induced activation.

It is contemplated that the same fluorophore/luminophore/quencher may be activated in one or more ways, or that multiple activation ways may be used sequentially or simultaneously.

In the present invention, the moiety capable of acting as a force-sensitive moiety/group/component can also be capable of generating a fluorophore and/or a luminophore and/or a quencher by other actions than mechanical forces, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, and the like. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.

In the present invention, when the energy donor and the energy acceptor are indirectly generated by the force-sensitive element/force-sensitive group/force-sensitive component/component, it may be that the force-sensitive element/force-sensitive group/force-sensitive component/component is activated to generate the energy donor and/or the energy acceptor from other structures, or that the activated product is regenerated into the energy donor and/or the acceptor by other actions after the force-sensitive element/force-sensitive group/force-sensitive component/component is activated. Fluorophores, luminophores and quenchers can all be generated directly and/or by force. The up-converted fluorescence may also serve as excitation light, the fluorescence of the fluorophore may also serve as excitation light for the up-converted fluorescence, and the luminescence of the luminophore may also serve as excitation light for the up-converted fluorescence.

The force-responsive component, which is not usually a polymer, can generate a force response by directly applying a mechanical force to the component, and can also generate a force response by blending the force-responsive component with the polymer under the action of a mechanical force, and the force-responsive component comprises but is not limited to a force-responsive crystal, a force-responsive assembly, a force-responsive aggregate and a force-responsive composition. The force-responsive component of the present invention acts as a filler, is blended with the polymer or polymer composition, and optionally produces a force-responsive response synergistically and/or orthogonally with the force-sensitive groups contained on the polymer chain.

In the invention, the force-responsive crystal is generally a small molecular dye crystal, which is not connected with a high molecular chain but can be connected with a low molecular chain (the molecular weight of the force-responsive crystal is generally less than 1000Da), and is generally formed by crystallization/self-assembly followed by crystallization, and under the action of mechanical force, the crystalline state/assembly state of the force-responsive crystal is changed to generate changes of color, fluorescence, luminescence and the like, so that force response is realized; typical structures of the compounds include small molecule crystals such as spiropyran, spirothiopyran, spirooxazine, spirothiazine, rhodamine, etc., crystalline small molecule assemblies, small molecule aggregates, and small molecule compositions.

In the present invention, the force-responsive assembly, which is generally a non-crystalline small-molecule self-assembly, is not linked to a polymer chain, but may be linked to a low molecular chain (whose molecular weight is generally less than 1000Da), may be selected from donor-acceptor type, diketopyrrolopyrrole type, conjugated type, platinum coordination type, gold coordination type, beryllium coordination type, copper coordination type, iridium coordination type, boron coordination type, phenothiazine type, dioxaborolane type, dye molecule type; the typical structure of which can be referred to the structure described in the present invention in the previous paragraph based on non-covalent single force sensitive groups of supramolecular assemblies.

In the present invention, the force-responsive aggregate, which is generally an amorphous small-molecule aggregate, is not linked to a high-molecular chain, but may be linked to a low-molecular chain (whose molecular weight is generally less than 1000Da), and may be selected from the group consisting of a divinylanthracene type, a tetraarylethylene type, a cyanoethylene type, a berberine type, a maleimide type, a 4-hydropyran type; the typical structure of which can be referred to as the structure described in the invention above for the non-covalent aggregate-based force-sensitive groups.

In the present invention, the force-responsive composition, which generally comprises both non-crystalline small molecule energy donor and small molecule energy acceptor, is not linked to the high molecular chain, but can be linked to the low molecular chain (whose molecular weight is generally less than 1000Da), and the typical structure thereof can be referred to the description of the energy donor and energy acceptor in the non-covalent force-sensitive group based on the energy transfer composition in the present invention. Fluorophores that can be used as energy donors or energy acceptors include, but are not limited to, organic fluorophores, organometallic fluorophores, organoelement fluorophores, biological fluorophores, and inorganic fluorophores, and can be selected from pre-existing fluorophores, chemically activated fluorophores, biologically activated fluorophores, photoactivated fluorophores, thermally activated fluorophores, electrically activated fluorophores, and magnetically activated fluorophores.

In the present invention, chemical changes and supramolecular chemical changes are preferred, and chemical changes are more preferred when mechanical forces cause chemical and/or physical changes in the force sensitive group/force responsive component.

In addition, in the present invention, it is also possible to obtain a force response by introducing groups and/or components having anisotropy, which form an anisotropic structure after the polymer is stretched, and by generating a color depending on the degree of anisotropy under polarized light. The invention also does not exclude that the polymer is coated by the particle materials with certain optical characteristics, such as silica nano-particles, and the like, and the distance between the particle materials is changed under the stretching action, so that the scattering and the like on the surface of the polymer material are changed to generate color change. The invention also does not exclude the adoption of a polymer structure with phase separation performance, and the color change caused by light reflection/scattering between different phases and/or phase interfaces generated by phase separation is caused.

In the invention, the skin-carrying polymer foam particles prepared by covalently connecting the force sensitive groups on the polymer chain are utilized, because the force sensitive groups in the polymer are directly covalently connected with the polymer chain, the stress response condition on the polymer chain can be directly reflected under the action of mechanical force, even sensitive force responsiveness is shown, and meanwhile, the controllable adjustment of the force response effect can be realized by adjusting the type, the position and the number of the force sensitive groups in the polymer; the skinned polymer foam particles prepared by physically blending at least one force response component in the polymer can have a force response mode and effect and an application scene different from those of a force sensitive group, can be used independently or jointly with the force sensitive group, obtain a unique effect of the physically blended force response component or supplement the use limitation of the force sensitive group or achieve an orthogonal and synergistic effect, and can achieve an unexpected effect by organic reasonable regulation and control in the invention.

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, the cyclic group structure can be a micromolecular ring or a macromolecule ring, and the cyclic group structure is preferably a 3-50-membered ring, and more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on each ring-forming atom may or may not be substituted; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; whereinThe skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite; it has the characteristic of difficult crystallization and is beneficial to forming strong dynamic hydrogen bonds.

In the present invention, the topology of the expandable and dynamic polymers may be selected from the group consisting of linear, cyclic, branched, clustered, crosslinked, and combinations thereof.

In the embodiment of the present invention, for the expandable polymer and the dynamic polymer of the non-crosslinked structure, it may contain one or more non-crosslinked polymers. When a plurality of non-crosslinked polymers are contained, the non-crosslinked polymers can be mutually blended to form discontinuous, partially continuous or bicontinuous dispersed phases, can be mutually entangled to form compatible homogeneous structures, and can also form incompatible phase separation structures; non-crosslinked polymers may have non-covalent interactions between them.

In the embodiment of the present invention, as for the expandable polymer and the dynamic polymer of the crosslinked structure, it may contain only one crosslinked network (single network structure) or may contain a plurality of crosslinked networks (multi-network structure). When the polymer contains two or more crosslinked networks, the two or more crosslinked networks can be blended with each other, can be mutually interpenetrated, can be partially interpenetrated, and can also be a combination of the three cases, but the invention is not limited to the crosslinked networks; wherein two or more crosslinked networks may be the same or different. For expandable polymers, the crosslinked network can be formed by common covalent bonds and at least one of force sensitive groups, dynamic covalent bonds and supermolecule actions; or a part of cross-linked network only forms common covalent cross-linking by common covalent bonds, a part of cross-linked network only forms force-sensitive group cross-linking by force-sensitive groups and common covalent bonds, a part of cross-linked network only forms dynamic covalent cross-linking by dynamic covalent bonds and common covalent bonds, and a part of cross-linked network only forms supramolecular interaction cross-linking by supramolecular interaction and common covalent bonds, but the invention is not limited to the above; any cross-linked network can also form hybrid cross-linking by common covalent bond and at least one of force sensitive group, dynamic covalent bond and supermolecule action. For dynamic polymers, the crosslinked network therein may be selected to form crosslinks by suitable ordinary covalent bonds, dynamic covalent bonds, supramolecular interactions, and combinations thereof; wherein part of the crosslinked network can form dynamic covalent crosslinks only by dynamic covalent bonds and common covalent bonds, and part of the crosslinked network can form supramolecular interaction crosslinks only by supramolecular interaction and common covalent bonds, but the invention is not limited thereto; any one of the cross-linked networks may also form cross-links by ordinary covalent bonds, dynamic covalent bonds, supramolecular interactions, simultaneously. In embodiments of the present invention, the cross-linked network structures of the expandable polymer and the dynamic polymer may also be blended and/or interpenetrated with one or more other non-cross-linked polymers.

In embodiments of the invention, the degree of crosslinking of any one crosslink of any one network of the expandable polymer and dynamic polymer can also be reasonably controlled. When at least one crosslinking component is present, the different components (including the crosslinking component and the non-crosslinking component) may be dispersed, interspersed or partially interspersed with each other, but the present invention is not limited thereto. In the present invention, when the expandable polymer and the dynamic polymer contain at least two networks, the network having a higher degree of crosslinking may become a gate of the network having a lower degree of crosslinking, and the network having a lower degree of crosslinking may become a tether of the network having a higher degree of crosslinking. These properties are not achievable by the prior art and have unexpected results.

In embodiments of the invention, the expandable polymers and dynamic polymers may contain the force sensitive groups, dynamic covalent bonds, and supramolecular motifs/supramolecular interactions in any suitable location of the polymer; the various functions in the polymer can be independent or synergistic. For non-crosslinked polymers, the polymer not only can contain force-sensitive groups, dynamic covalent bonds and supramolecular motifs/supramolecular actions on the backbone of the polymer main chain, but also can contain force-sensitive groups, dynamic covalent bonds and supramolecular motifs/supramolecular actions on the side chain/branch chain/branched chain backbone of the polymer; for the cross-linked polymer, the force sensitive group, the dynamic covalent bond and the supramolecular unit/supramolecular action can be contained on the framework of a cross-linked network chain (main chain), and the force sensitive group, the dynamic covalent bond and the supramolecular unit/supramolecular action can be contained on the framework of a side chain/branched chain of the cross-linked network chain; the invention also does not exclude the presence of force-sensitive groups, dynamic covalent bonds and supramolecular motifs/interactions on the side and/or end groups of the polymer chain, on other constituents of the polymer, such as small molecules, fillers, etc. In embodiments of the present invention, the force sensitive groups, dynamic covalent bonds, supramolecular motifs are preferably located on the backbone of the polymer backbone (for non-crosslinked structures) and on the backbone of the polymer crosslinked network chains (for crosslinked structures).

According to a preferred embodiment of the present invention, the dynamic polymer comprises at least one dynamic covalent bond in its polymer chain; the skinned polymeric foam particles comprise at least one dynamic covalent bond and/or at least one supramolecular interaction in their polymer chains. In the embodiment, dynamic components are introduced into the polymer foam particles, so that the polymer foam particles have dynamic characteristics, and due to the fact that the dynamic property of the supramolecular action is rich and adjustable, the dynamic properties such as dynamic dilatancy, self-repairability, super toughness, shape memory property, recyclability and the like can be obtained, and the composite material has good processing formability and reuse characteristics.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles comprise at least one dynamic covalent bond and/or at least one supramolecular interaction in their polymer chains. In the embodiment, different dynamic components are introduced into the dynamic polymer and the polymer foam particles, so that the dynamic property of the composite material has an orthogonal and/or synergistic effect, the composite material is favorable for performing quick and efficient self-repairing and dynamic response on the composite material, and more efficient and abundant dynamic properties and energy absorption capacity are obtained.

According to a preferred embodiment of the invention, the dynamic polymer contains at least two supramolecular interactions in its polymer chain; the skinned polymeric foam particles comprise at least one dynamic covalent bond and/or at least one supramolecular interaction in their polymer chains. In the embodiment, different dynamic components are introduced into the dynamic polymer and the polymer foam particles, so that the dynamic property of the composite material has an orthogonal and/or synergistic effect, the composite material is favorable for performing quick and efficient self-repairing and dynamic response on the composite material, and more efficient and abundant dynamic properties and energy absorption capacity are obtained.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles comprise at least one dynamic covalent bond in their polymer chain. In the embodiment, different dynamic components are introduced into the dynamic polymer and the polymer foam particles, so that the dynamic property of the composite material has an orthogonal and/or synergistic effect, the composite material is favorable for performing quick and efficient self-repairing and dynamic response on the composite material, and more efficient and abundant dynamic properties and energy absorption capacity are obtained.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles contain at least one dynamic covalent bond and at least one supramolecular interaction in their polymer chains. In the embodiment, different dynamic components are introduced into the dynamic polymer and the polymer foam particles, so that the dynamic property of the composite material has an orthogonal and/or synergistic effect, the composite material is favorable for performing quick and efficient self-repairing and dynamic response on the composite material, and more efficient and abundant dynamic properties and energy absorption capacity are obtained.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles contain at least one force-sensitive group in their polymer chain. In this embodiment, by introducing the force-sensitive groups into the polymer foam particles, the force-sensitive groups in the foam particles can be directly linked with the polymer chains through covalent and/or non-covalent, and the stress response condition on the polymer chains can be directly reflected under the action of mechanical force, so that even more sensitive force response is shown.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; the skinned polymer foam particles have at least one force-responsive component blended into the polymer. In this embodiment, due to the physical blending of the force-responsive component in the polymer foam particles, a force-responsive manner and effect and application scenario different from that of the force-sensitive groups can be provided, which supplements the use limitations of the force-sensitive groups or achieves an orthogonal, synergistic effect, so that the composite material obtains different force-responsiveness.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles contain at least one force-sensitive group in the polymer chain and at least one force-responsive component blended in the polymer. In the embodiment, the force-sensitive groups and the force-responsive components are simultaneously introduced into the polymer foam particles, so that the force responsiveness of the polymer foam particles has orthogonal and/or synergistic effects, and the composite material is beneficial to obtaining more efficient and abundant dynamic characteristics and force responsiveness.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; the skinned polymer foam particles are dilatant. In this embodiment, the skinned polymeric foam particles having dilatancy properties are selected such that the polymeric foam particles achieve high efficiency, rich dilatancy and energy absorption characteristics.

According to a preferred embodiment of the invention, the dynamic polymer is a non-crosslinked structure. In this embodiment, since the dynamic polymer is a non-crosslinked structure, a rapid dilatant response is possible while being suitable for increasing viscous loss to absorb energy.

According to a preferred embodiment of the invention, the dynamic polymer contains supramolecular cross-links. In the embodiment, as the dynamic polymer contains a supermolecular interaction crosslinking structure, the dynamic polymer can be provided with noncovalent property and self-supporting property, and is convenient to self-repair and recycle.

According to a preferred embodiment of the invention, the dynamic polymer contains dynamic covalent cross-links. In this embodiment, since the dynamic polymer contains a dynamic covalent cross-linked structure, it is possible to provide dynamic covalent characteristics to the dynamic polymer, facilitating self-repair and recycling.

According to a preferred embodiment of the invention, the dynamic polymer contains conventional covalent cross-links. In this embodiment, since the dynamic polymer contains a common covalent cross-linked structure, it is possible to provide a balanced structure and mechanical properties to the composite material, and to achieve organic coordination of mechanical properties and force responsiveness.

According to a preferred embodiment of the present invention, the dynamic polymer contains at least two of ordinary covalent crosslinking, dynamic covalent crosslinking, and supramolecular interaction crosslinking. In this embodiment, since the dynamic polymer contains a hybrid cross-linked structure, by combining different dynamic/non-dynamic units, the advantages of each can be fully exerted, and a synergistic effect can be achieved, so that organic coordination of mechanical properties and dynamics is achieved.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; the skinned polymeric foam particles are formed by chemical crosslinking. In this embodiment, since the polymeric foam particles are formed by chemical crosslinking, the foam particles can be provided with covalent character and an equilibrium structure.

According to a preferred embodiment of the invention, the dynamic polymer is a foamed structure. In this embodiment, since the dynamic polymer is also a foamed structure, it can form a syntactic foam together with the polymer foam particles, and the foam structures in the different phases can act orthogonally and/or synergistically.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; wherein the polymer constituting the skinned polymeric foam particles is a thermoplastic plastomer. In the embodiment, the thermoplastic plastomer is selected as the matrix of the polymer foam particles, so that the foam particles have excellent mechanical properties and dimensional stability, can be subjected to die forging, stamping and extrusion, and have strong impact resistance, vibration resistance and deformation resistance.

According to a preferred embodiment of the invention, the dynamic polymer comprises at least one dynamic covalent bond and/or at least one supramolecular interaction in its polymer chain; wherein the polymer constituting the skinned polymer foam particles is a thermoplastic elastomer. In this embodiment, the thermoplastic elastomer is selected as the matrix of the polymer foam particles, which can make the foam particles have the characteristics of high strength, high resilience, soft touch, excellent weather resistance, fatigue resistance and temperature resistance, etc.

In a preferred embodiment of the invention, the skinned polymer foam particles that constitute the composite material are prepared from a thermoplastic plastomer, a blowing agent and optionally further auxiliaries and optionally fillers.

Compared with a thermoplastic elastomer, the thermoplastic elastomer has excellent mechanical properties and dimensional stability, can be subjected to die forging, stamping and extrusion, and has strong impact resistance, vibration resistance and deformation resistance.

In an embodiment of the present invention, the thermoplastic plastomer, which is processed by using thermoplastic equipment, includes but is not limited to polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyacrylic acid, polyacrylamide, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polytetrahydrofuran, polycaprolactone, polylactide, polycarbonate, polyorganosilane, and polyorganosiloxane.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one dynamic covalent bond and/or at least one supramolecular interaction in the thermoplastic plastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one force-sensitive group and/or at least one force-responsive component blended therein.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and also contains common covalent crosslinks formed by common covalent bonds in the thermoplastic plastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and the thermoplastic plastomer has dilatancy.

In a preferred embodiment of the invention, the skinned polymer foam particles that constitute the composite material are prepared from a thermoplastic elastomer, a blowing agent and optionally further auxiliaries and optionally fillers.

The thermoplastic elastomer has the characteristics of high strength, high resilience, soft touch, excellent weather resistance, fatigue resistance and temperature resistance, excellent colorability and excellent processability, and is wide in application range, environment-friendly, non-toxic and safe.

In an embodiment of the present invention, the thermoplastic elastomer is processed by using thermoplastic equipment, and includes, but is not limited to, styrenes (SBS, SIS, SEBS, SEPS), olefins (TP0, TPV), dienes (TPB, TPI), vinyl chlorides (TPVC, TCPE), polyurethanes (TPU), polyesters (TPEE), polyamides (TPEE), organic fluorine compounds (TPF), and silicones.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one dynamic covalent bond and/or at least one supramolecular interaction in the thermoplastic elastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one force-sensitive group is also contained in the thermoplastic elastomer and/or at least one force-responsive component is blended therein.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and also contains common covalent crosslinks formed by common covalent bonds in the thermoplastic elastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermoplastic elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and the thermoplastic elastomer has dilatancy.

In a preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting plastomer, a blowing agent and optionally further auxiliaries and optionally fillers.

Compared with a thermoplastic plastomer, the thermosetting plastomer has excellent hardness and mechanical strength, high rigidity, higher heat resistance and higher compression deformation resistance.

In an embodiment of the present invention, the thermosetting plastic body, which is processed by using thermosetting equipment, includes, but is not limited to, epoxy resin, phenolic resin, urea resin, amino resin, unsaturated polyester, alkyd resin, and silicone resin.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one dynamic covalent bond and/or at least one supramolecular interaction in the thermoset plastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one force-sensitive group, and/or at least one force-responsive component blended therein, in a thermoset plastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and also contains common covalent crosslinks formed by common covalent bonds in the thermoset plastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting plastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and the thermosetting plastic body has dilatancy.

In a preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting elastomer, a blowing agent and optionally further auxiliaries, optionally fillers.

Compared to thermoset plastomers, thermoset elastomers have high resilience properties.

In an embodiment of the present invention, the thermosetting elastomer is processed by using thermosetting equipment, and includes but is not limited to thermosettable epdm, nitrile butadiene rubber, neoprene rubber, silicone-based rubber, and unsaturated polyurethane.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one dynamic covalent bond and/or at least one supramolecular interaction in the thermoset elastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and at least one force-sensitive group is also contained in the thermosetting elastomer and/or at least one force-responsive component is blended therein.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and also contains common covalent crosslinks formed by common covalent bonds in the thermoset elastomer.

In a more preferred embodiment of the invention, the skinned polymeric foam particles that constitute the composite material are prepared from a thermosetting elastomer, a blowing agent and optionally further auxiliaries, optionally fillers; and the thermosetting elastomer has dilatancy.

In the present invention, the dynamic polymer matrix in addition to the polymer foam particles in the composite may also be foamed into a foam to form a foam having a foamed matrix blended with the polymer foam particles. The dynamic polymer matrix (composition) may also contain auxiliaries, fillers, etc.

In the present invention, the foaming agent can foam the polymer sample into pores, and includes, but is not limited to, any one or more of the following foaming agents: physical blowing agents, including hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, acetals, etc., such as air, nitrogen, ammonia, carbon dioxide, water, propane, methyl ether, butane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, octane, petroleum ether, acetone, benzene, toluene, diethyl ether, methyl chloride, methylene chloride, ethylene dichloride, difluoromethane, chlorotrifluoromethane, perfluorohexane, chlorofluorocarbons, wherein said physical blowing agent, which may also be selected from supercritical gases such as supercritical carbon dioxide, nitrogen, ethane, ethylene, propane, toluene, etc.; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylenetetramine, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azobisisobutyronitrile, 4 ' -oxybis-benzenesulfonylhydrazide, trihydrazinotriazine, p-toluenesulfonylaminourea, biphenyl-4, 4 ' -disulfonylazide; hollow/expandable microspheres such as Expancel microspheres from akksonobel, Polychem Alloy expanded microspheres from usa, expandable microspheres from japan somnolipid pharmaceutical co; foaming promoters such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc. Among them, the foaming agent is preferably a physical foaming agent, hollow microspheres/expandable microspheres, and the amount of the foaming agent used is not particularly limited, but is generally 0.1 to 40% by weight, preferably 0.5 to 35% by weight, and more preferably 1 to 30% by weight.

In the present invention, the foaming agent selected may vary depending on the method of preparing the material. When the polymer foam particles are prepared by the suspension method, the blowing agent used preferably comprises an organic liquid or an inorganic gas or a mixture thereof, more preferably a saturated aliphatic hydrocarbon having 3 to 8 carbon atoms. When the polymer foam particles are prepared by extrusion, the blowing agents used preferably comprise volatile organic compounds (boiling point-25 to 150 ℃, especially-10 to 150 ℃), in particular paraffins having 4 to 10 carbon atoms, such as butane, pentane, hexane, heptane and octane and isomers thereof, with secondary pentane being especially preferred, and other suitable blowing agents may be selected from compounds having a larger self-volume, such as alcohols, ketones, esters, ethers and organic carbonates, etc. During the use of the foaming agent, a proper amount of foam stabilizer and foam pore regulator can be added to help the raw material to be homogenized and regulate the cell structure. Suitable foam stabilizers include, but are not limited to, dihydroxypropyl octadecanoate, sorbitan monolaurate, sorbitan palmitate, sorbitan stearate monoester, sucrose fatty acid esters, siloxane-oxyalkylene copolymers, organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil, ricinoleate, turkey red oil, peanut oil, and the like; suitable cell regulators include, but are not limited to, paraffin, fatty alcohols, dimethylpolysiloxanes, and the like. Sodium castor oil sulfate or fatty acid salts, and salts of fatty acids with amines, such as diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate; salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzenedisulfonic acid or dinaphthylmethanedisulfonic acid and ricinoleic acid; oligomeric polyacrylates having polyoxyalkylene and fluoroalkyl groups as side groups are also suitable for use in the system, and serve to improve emulsification, regulate cell structure, and stabilize the foam.

In the invention, the optional other auxiliary agents can improve the material preparation process, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance. The other auxiliary agents are selected from any one or more of the following components: the synthesis auxiliary agent comprises a catalyst and an initiator; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; the auxiliary agent for improving the mechanical property comprises a cross-linking agent, a curing agent, a toughening agent, a chain extender and a compatilizer; the processing performance improving additives comprise a lubricant and a release agent; softening and lightening auxiliaries, including plasticizers; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant additives, including flame retardants.

Wherein the optional catalyst for synthesis, which is generally used in the synthesis reaction of a polymer in a chemical foaming process to accelerate the reaction rate by catalyzing the reaction between reactive groups and to accelerate the polymerization of the polymer, includes, but is not limited to, any one or more of ① catalysts for polyurethane synthesis, such as amine catalysts, e.g., triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N ' -trimethyl-N ' -hydroxyethyldimethylaminoethylethyl ether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N-dimethylethyleneethanolamine, N-ethylmorpholine, 2, 4, 6- (dimethylaminomethyl) phenol, dibutyltin-2-hexanoate, N, N, N-dimethylborazine, N ' -pentamethyldiethylenetriamine, N, N ' -dimethylborazine, potassium octoate, sodium chloride, sodium octylate, sodium chloride, potassium octylate, sodium chloride, potassium octylaluminum chloride, sodium chloride, potassium octylate, sodium chloride, sodium aluminum chloride, sodium chlorideCan be selected from Cu (I) salts such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; may also be selected from Cu (I) complexes, e.g. [ Cu (CH)₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, and the like. The amount of the catalyst to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.

Wherein the optional initiator is capable of causing the monomer molecules to activate to generate free radicals during the polymerization reaction, thereby increasing the reaction rate and promoting the reaction, and includes, but is not limited to, ① radical polymerization initiator selected from organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butylperoxide, diisopropylbenzene hydroperoxide, azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides such as ammonium persulfate, potassium persulfate, etc., ② polymerization initiator selected from 2, 2, 6, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine ternary system, etc., ③ ionic polymerization initiator selected from butyllithium, sodium/naphthalene system, boron trifluoride/water system, stannic chloride/haloalkane system, ④ coordination initiator selected from aluminum/copper chloride/bipyridine ternary system, titanium tetrachloride, and the like, preferably, 2, 5-methyl-bis (4-butyl) ammonium persulfate, potassium persulfate, and the like, wherein the amount of the initiator selected from the initiator is preferably 0.7 molar ratio of lauroyl-bis (2, 5) of ethylene peroxide, 2, 5, 539, 2, 5, 2, 5, 2, 3.

The optional antioxidant can retard the oxidation process of the polymer sample and ensure that the material can be processed smoothly and the service life of the material can be prolonged, including, but not limited to, any one or more of hindered phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 ' -methylenebis (4-methyl-6-tert-butylphenol), sulfur-containing hindered phenols such as 4, 4 ' -thiobis- [ 3-methyl-6-tert-butylphenol ], 2 ' -thiobis- [ 4-methyl-6-tert-butylphenol ], triazine-based hindered phenols such as 1, 3, 5-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, tri-isocyanate hindered phenols such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate, N-bis [3, 5-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, tri-butyl-4-tert-phenylenediamine, N-butyl-4-hydroxy-phenyl phosphite, N-bis [3, 5-4-hydroxyphenyl ] naphthalene ] tris (3, 5-butyl-4-hydroxy-butyl-4-phenyl) phosphite, 3, 5-tert-butyl-4-hydroxy-phenyl) phosphite, 3, 5-phenyl) tris (tert-butyl-4-phenyl) phosphite, 3, 5-phenyl) phosphite, 5-tert-butyl-phenyl) phosphite, 2 ' -bis (2-4-phenyl) phosphite, 3-butyl-4-tert-butyl-phenyl) phosphite, 3-butyl-tert-butyl-phenyl) phosphite, 2-butyl-4-butyl-phenyl phosphite, 2 ' -bis (4-tert-butyl.

Wherein, the optional light stabilizer can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and the optional light stabilizer comprises any one or more of the following light stabilizers: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2, 4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1, 3, 5-s-triazine, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; precursor type ultraviolet absorbers such as p-tert-butyl benzoate salicylate, bisphenol A disalicylate; ultraviolet ray quenchers, such as bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel; hindered amine light stabilizers such as bis (2, 2, 6, 6-tetramethylpiperidine) sebacate, 2, 2, 6, 6-tetramethylpiperidine benzoate, tris (1, 2, 2, 6, 6-pentamethylpiperidyl) phosphite; other light stabilizers, such as 2, 4-di-tert-butyl-4-hydroxybenzoic acid (2, 4-di-tert-butylphenyl) ester, alkylphosphoric acid amide, zinc N, N '-di-N-butyldithiocarbamate, nickel N, N' -di-N-butyldithiocarbamate, etc.; among them, carbon black and bis (2, 2, 6, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.

Wherein, the optional heat stabilizer can prevent the polymer sample from generating chemical changes due to heat during processing or use, or delay the changes to achieve the purpose of prolonging the service life, and includes but is not limited to any one or any several of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, isooctyl dimethyltin dimercaptoacetate; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di (n) -butyltin maleate are preferable as the heat stabilizer. The amount of the heat stabilizer to be used is not particularly limited, but is usually 0.1 to 0.5% by weight.

The optional cross-linking agent is used by being matched with a reactant component needing to be cross-linked in the polymer, can play a bridging role among linear polymer molecules, enables a plurality of linear molecules to be mutually bonded and cross-linked to form a network structure, can further increase the cross-linking density and cross-linking strength of the polymer, improves the heat resistance and service life of the polymer, and simultaneously improves the mechanical property and weather resistance of the material, and comprises any one or more than one of the following cross-linking agents: polypropylene glycol glycidyl ether, zinc oxide, aluminum chloride, aluminum sulfate, chromium nitrate, ethyl orthosilicate, methyl orthosilicate, p-toluenesulfonic acid, p-toluenesulfonyl chloride, 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, aluminum isopropoxide, zinc acetate, titanium acetylacetonate, aziridine, phenol resin, hexamethylenetetramine, dicumyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, cyclohexanone peroxide, acetophenone peroxide, di-t-butyl phthalate, cumene hydroperoxide, vinyltri-t-butylperoxysilane, diphenyl-di-t-butylperoxysilane, trimethyl-t-butylperoxysilane, and the like. Among them, dicumyl peroxide (DCP), Benzoyl Peroxide (BPO) and 2, 4-dichlorobenzoyl peroxide (DCBP) are preferable as the crosslinking agent. The amount of the crosslinking agent to be used is not particularly limited, but is generally 0.1 to 5% by weight.

The optional curing agent is used by being matched with a reactant component needing to be cured in the polymer, and can promote or control the curing reaction of the reactant component in the polymerization process, and the optional curing agent comprises any one or more of the following curing agents: amine curing agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylenediamine; acid anhydride curing agents such as phthalic anhydride, maleic anhydride, pyromellitic dianhydride; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; boron trifluoride complex, and the like. Among them, Ethylene Diamine (EDA), Diethylenetriamine (DETA), phthalic anhydride and maleic anhydride are preferable as the curing agent, and the amount of the curing agent to be used is not particularly limited, but is usually 0.5 to 1% by weight.

The optional toughening agent can reduce the brittleness of a polymer sample, increase the toughness and improve the bearing strength of the material, and comprises any one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS) or chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited, but is generally 5 to 10% by weight.

The optional chain extender can react with functional groups on a linear polymer chain to expand a molecular chain and increase molecular weight, can be used for improving the mechanical property and the process property of products such as polyurethane, polyester and the like, can be an oligomer with active hydrogen, can also be a small molecular compound with active hydrogen, and comprises but is not limited to any one or more of the following chain extenders: ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), resorcinol dihydroxyethyl ether (HER), p-bis-hydroxyethyl bisphenol A, triethanolamine, triisopropanolamine, diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tetraethyldiphenylmethylenediamine, tetraisopropyldiphenylenediamine, m-phenylenediamine, tris (dimethylaminomethyl) phenol, diaminodiphenylmethane, 3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), 3, 5-dimethylthiotoluenediamine (DMTDA), 3, 5-diethyltoluenediamine (DETDA), 1, 3, 5-triethyl-2, 6-diaminobenzene (TEMPDA); among them, the chain extender is preferably a small molecular compound with active hydrogen, such as small molecular polyamine, polyol, polythiol, alcohol amine, water and the like. The amount of the chain extender to be used is not particularly limited, and is generally 0.1 to 25% by weight.

Wherein the compatibilizer, which can improve interfacial properties between polymer samples or with inorganic fillers or reinforcing materials by virtue of intermolecular bonding force, thereby obtaining a stable blend, can reduce viscosity of material melt during plastic processing, improve dispersibility of fillers to improve processability, thereby obtaining good surface quality and mechanical, thermal and electrical properties of the product, includes but is not limited to any one or more of coupling agent type compatibilizers including organic acid chromium complex, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent, zirconate coupling agent, and the like, such as divinyl tetramethyl disiloxane, vinyl triethoxy siloxane, vinyl trichlorosilane, vinyl tris (β -methoxyethoxy) silane, gamma-glycidoxypropyl-trimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, N- (β -aminoethyl) -gamma-aminopropyl-methyl-trimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropyl) trimethoxysilane, gamma-methyl-trimethoxysilane, gamma-aminopropyl-trimethoxysilane, gamma-polyoxyethylene-.

Wherein the optional lubricant can improve the lubricity, reduce friction, and reduce interfacial adhesion of the polymer sample, and includes but is not limited to any one or more of the following lubricants: saturated and halogenated hydrocarbons, such as paraffin wax, microcrystalline wax, liquid paraffin wax, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters such as fatty acid lower alcohol esters, fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides, such as stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylene bis stearamide; fatty alcohols, such as stearyl alcohol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc.; among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, low molecular weight polyethylene. The amount of the lubricant used is not particularly limited, but is generally 0.5 to 1% by weight.

Wherein, the optional release agent can make the polymer sample easy to release, smooth and clean, and includes but is not limited to any one or more of the following release agents: paraffin, soaps, dimethyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicone rubber and the like; among them, the release agent is preferably dimethyl silicone oil. The amount of the release agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.

Wherein the optional plasticizer, which can increase the plasticity of the polymer sample, reduces the hardness, modulus, softening temperature and brittle temperature of the polymer, and improves the elongation, flexibility and flexibility, includes but is not limited to any one or any several of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalateDiheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, such as epoxyglycerides, epoxidized fatty acid monoesters, epoxidized tetrahydrophthalic acid esters, epoxidized soybean oil, epoxidized 2-ethylhexyl stearate, epoxidized 2-ethylhexyl soyate, 4, 5-epoxytetrahydrophthalic acid di (2-ethyl) hexyl ester, and methyl chrysene acetyl ricinoleate; glycol esters, e.g. C_5～9Acid ethylene glycol ester, C_5～9Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol-series ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester, phenyl petroleum sulfonate, trimellitate ester, citrate ester and the like; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited, but is generally 5 to 20% by weight.

Wherein, the optional antistatic agent can guide or eliminate the harmful charges accumulated in the polymer sample, so that the polymer sample does not cause inconvenience or harm to production and life, and the optional antistatic agent comprises any one or more of the following antistatic agents: anionic antistatic agents such as alkylsulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate ester diethanolamine salts, potassium p-nonylphenyl ether sulfonates, phosphate ester derivatives, phosphates, phosphate ester derivatives, fatty amine sulfonates, sodium butyrate sulfonates; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium ethyl inner salt, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine ethyl inner salt, N-lauryl-N, N-dipolyoxyethylene-N-ethylphosphonic acid sodium salt, N-alkyl amino acid salts; nonionic antistatic agents such as fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene ether phosphate esters, glycerin fatty acid esters; high molecular antistatic agents such as polyallylamine N-quaternary ammonium salt substitutes, poly-4-vinyl-1-acetonylpyridinophosphoric acid-p-butylbenzene ester salts, and the like; among them, lauryl trimethyl ammonium chloride and alkyl phosphate diethanol amine salt (antistatic agent P) are preferable as the antistatic agent. The amount of the antistatic agent to be used is not particularly limited, but is generally 0.3 to 3% by weight.

Wherein, the optional emulsifier can improve the surface tension between various constituent phases in the polymer mixed solution containing the auxiliary agent, so that a uniform and stable dispersion system or emulsion is formed, and the optional emulsifier is preferably used for carrying out emulsion polymerization and comprises any one or more of the following emulsifiers: anionic type, such as higher fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, sodium alkylnaphthalenesulfonate, succinic acid ester sulfonate, petroleum sulfonic acid salts, castor oil sulfate ester salts, sulfated ricinoleic acid butyl ester salts, phosphate ester salts, fatty acyl-peptide condensates; cationic, such as alkyl ammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic types such as alkylphenol ethoxylates, polyoxyethylene fatty acid esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol and sorbitan fatty acid esters, sucrose fatty acid esters, alcohol amine fatty acid amides, and the like; the emulsifier is preferably sodium dodecyl benzene sulfonate, sorbitan fatty acid ester, and triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited, but is generally 1 to 5% by weight.

The optional dispersant can disperse solid floccules in the polymer mixed solution into fine particles to be suspended in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously can prevent the particles from settling and coagulating to form a stable suspension, and includes but is not limited to any one or more dispersants: organic types such as polyvinyl alcohol, polyacrylic acid and polymethacrylic acid salts, sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium petroleum sulfonate, maleic anhydride-styrene copolymer, methyl cellulose, hydroxypropyl methyl cellulose, gelatin, sodium alginate, fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicates, carbonates, phosphates, etc.; among them, tricalcium phosphate, magnesium pyrophosphate, metal carbonate, polyvinyl alcohol and a surfactant, such as sodium dodecylbenzenesulfonate, are preferable as the dispersant. The amount of the dispersant used is not particularly limited, but is generally 0.05 to 10% by weight.

Wherein, the optional colorant can make the product present the required color and increase the surface color, and the optional colorant comprises any one or more of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. lithol rubine BK, lake Red C, perylene Red, Jia-base R Red, Phthalocyanine Red, permanent magenta HF3C, Plastic scarlet R and Clomomor Red BR, permanent orange HL, fast yellow G, Ciba Plastic yellow R, permanent yellow 3G, permanent yellow H₂G. Phthalocyanine blue B, phthalocyanine green, plastic purple RL and aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil-soluble yellow, etc.; the colorant is selected according to the color requirement of the sample, and is not particularly limited. The amount of the colorant to be used is not particularly limited, but is generally 0.01 to 5% by weight, more preferably 0.2 to 2% by weight.

In the present invention, the colorant may have the same concentration inside and outside the composite/polymer foam particle to exhibit a uniform color, or may exhibit different color gradients or color distributions. In the present invention, the skinned polymeric foam particles having at least two colors can be obtained by employing at least two colorants.

Wherein, the optional fluorescent whitening agent can enable the dyed materials to obtain the fluorite-like flash luminescence effect, and the optional fluorescent whitening agent comprises any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like; among the fluorescent whitening agents, sodium diphenylethylene disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1) are preferable. The amount of the fluorescent whitening agent to be used is not particularly limited, but is generally 0.002 to 0.03% by weight.

Wherein the optional matting agent is capable of causing diffuse reflection of incident light upon reaching the polymer surface, resulting in a low gloss matte and matte appearance, including but not limited to any one or more of the following: settling barium sulfate, silicon dioxide, hydrous gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited, but is generally 2 to 5% by weight.

Wherein, the optional flame retardant can increase the flame resistance of the material, and includes but is not limited to any one or more of the following flame retardants: phosphorus series such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as high chlorine content chlorinated paraffins, 1, 2, 2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorendic anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like; among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and antimony trioxide are preferable as the flame retardant. The amount of the flame retardant to be used is not particularly limited, but is generally 1 to 20% by weight.

In the preparation process of the polymer foam particles, other optional auxiliary agents are preferably antioxidants, light stabilizers, heat stabilizers, crosslinking agents, chain extenders, compatibilizers, toughening agents, plasticizers and flame retardants.

In the invention, the optional filler mainly plays a role in the polymer, such as ① reduction of shrinkage rate of a formed product, improvement of dimensional stability, surface smoothness, flatness or dullness of the product and the like, ② adjustment of viscosity of the polymer, ③ meeting different performance requirements, such as improvement of impact strength, compression strength, hardness, rigidity and modulus of a polymer material, improvement of wear resistance, improvement of heat deformation temperature, improvement of electrical conductivity and thermal conductivity and the like, ④ improvement of coloring effect of a pigment, ⑤ endowment of light stability and chemical corrosion resistance, ⑥ function of compatibilization, cost reduction and market competitiveness of the product are improved.

The optional fillers include, but are not limited to, inorganic non-metallic fillers, organic fillers, and organometallic compound fillers.

The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, molybdenum disulfide, silica, zinc oxide, alumina, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano silica, nano Fe₃O₄Particulate, nano gamma-Fe₂O₃Particulate, nano MgFe₂O₄Particulate, nano-MnFe₂O₄Granular, nano CoFe₂O₄Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)₄：Er、CaF₂：Er、Gd₂(M_oO₄)₃：Er、Y₂O₃：Er、Gd₂O₂S：Er、BaY₂F₈：Er、LiNbO₃：Er，Yb，Ln、Gd₂O₂：Er，Yb、Y₃Al₅O₁₂：Er，Yb、TiO₂：Er，Yb、YF₃：Er，Yb、Lu₂O₃：Yb，Tm、NaYF₄：Er，Yb、LaCl₃：Pr、NaGdF₄：Yb，Tm@NaGdF₄: core-shell nanostructure of Ln, NaYF₄：Yb，Tm、Y2BaZnO₅：Yb，Ho、NaYF₄：Yb，Er@NaYF₄: core-shell nanostructure of Yb and Tm, NaYF₄：Yb，Tm@NaGdF₄: a core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers, and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the heat generating function under the action of infrared and/or near-infrared light and/or electromagnetic is preferably selected from graphene, graphene oxide, carbon nanotube, nano-Fe₃O₄The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. Good heating performance, especially remote control heating performance, and is beneficial to obtaining controllable shape memory, self-repairing performance and the like. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.

The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-CoPt₃Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other infrared and near-infrared magnetic particlesNano metal particles which can generate heat under the action of at least one of ultraviolet and electromagnetism, and the like; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.

The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.

Wherein, the type of the added filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred₃O₄Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In embodiments of the invention, the filler may also optionally be modified byAnd then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the method has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.

In the preparation process of the composite material, the addition amount of each component raw material is not particularly limited, and can be adjusted by a person skilled in the art according to the actual preparation situation and the target polymer performance.

In the embodiments of the present invention, the process for preparing the dynamic polymer can be any suitable means in principle. Wherein, the preparation of dynamic polymers generally has two basic modes, starting from monomers containing dynamic covalent bonds/supramolecular motifs, and polymerizing with other optional monomers; or a prepolymer containing active points for subsequent reaction is synthesized, and dynamic covalent bonds/supramolecular motifs are introduced through a suitable chemical reaction. The dynamic polymers can also be prepared by a combination of the two ways described above, for example by first polymerizing monomers containing part of the functional groups, monomers containing reactive sites and optionally further monomers, and then introducing the desired remaining functional groups by suitable chemical reactions. Wherein, the active sites capable of subsequent reaction include, but are not limited to, amino groups, secondary amino groups, hydroxyl groups, carboxyl groups, mercapto groups, isocyanate groups, epoxy groups, ester groups, halogen atoms, acid halide groups, acid anhydrides, carbon-carbon double bonds, maleimide, carbon-carbon triple bonds, azide groups, nitrile groups, hydrazine, tetrazine, and succinimide esters.

In embodiments of the present invention, reactions that may be employed for the generation or introduction of dynamic covalent bonds/supramolecular motifs include, but are not limited to, the following types: esterification reaction, reaction of isocyanate and amino/hydroxyl/mercapto/carboxyl, electrophilic substitution reaction of heterocycle, nucleophilic substitution reaction of heterocycle, double bond (including acrylate, acrylamide and the like) free radical reaction, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester and amino; preferably, esterification reaction, reaction of isocyanate with amino/hydroxyl/mercapto, double bond free radical reaction, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, reaction of active ester with amino; more preferably, esterification reaction, reaction of isocyanate with amino/hydroxyl/mercapto group, double bond radical reaction, double bond addition reaction, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction. The generation or introduction of dynamic covalent bonds/supramolecular motifs may have one or more reaction types, means.

In the embodiment of the present invention, the polymer chain segment and/or the small molecule linker for connecting the dynamic covalent bond/supramolecular motif can be directly selected from commercial raw materials, or can be synthesized by any suitable chemical reaction or polymerization method.

In the present invention, the dynamic polymer used for preparing the composite material can be prepared by chemically reacting a certain proportion of reaction raw materials by any suitable mixing method known in the art. The mixing means used includes, but is not limited to, solution stirring mixing, melt stirring mixing, kneading, banburying, roll mixing, melt extrusion and the like, and among them, solution stirring mixing, melt stirring mixing and melt extrusion are preferable.

The specific process for preparing dynamic polymers by stirring and mixing solutions is usually to mix the raw materials in dissolved or dispersed form in the respective solvents or in a common solvent in a reactor by stirring and mixing. Generally, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mould and placed for 0-48h at the temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample; the dynamic polymer obtained can be chosen according to requirements to be present in the form of gel, plate, granule or other form, preferably in the form of granules.

The specific method for preparing dynamic polymer by melt-stirring mixing is usually to directly stir and mix the raw materials in a reactor or to stir and mix the raw materials after heating and melting, and this method is generally used in the case that the raw materials are gas, liquid or solid with a low melting point. Generally, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mould and placed for 0-48h at the temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample; the dynamic polymer obtained can be chosen according to requirements to be present in the form of gel, plate, granule or other form, preferably in the form of granules.

The specific method for preparing dynamic polymer by melt extrusion mixing is to add raw materials into an extruder to carry out extrusion blending reaction, wherein the extrusion temperature is 0-280 ℃, and preferably 50-150 ℃. The extruded reaction product can be directly used after being cut into granules, or cut into a proper size after being cast, or a sample is prepared by an injection molding machine or a molding press, and preferably is directly used after being cut into granules.

In the invention, the prepared dynamic polymer in a non-granular form can be cut, crushed and granulated to obtain dynamic polymer granules, and the cutting adopted can be any suitable cutting method; the pulverization is preferably carried out at low temperature freezing; the granulation is preferably extrusion foaming into a strip-shaped foaming material, and then cutting granulation is carried out at an extrusion die.

In the process of preparing the polymer foam particles according to the present invention, it is preferable to prepare the polymer foam particles by a physical foaming method, a chemical foaming method, or a 3D printing method, and the foaming is completed when the preparation of the polymer foam particles with the skin is completed.

Wherein, the physical foaming method is to realize the foaming of the polymer particles to be foamed by utilizing the physical principle in the preparation process of the foam particles, and the method comprises the following methods: (1) inert gas foaming, i.e., pressing inert gas into molten polymer particles under pressure, then decompressing and heating up in the course of granulation or the like, so that the dissolved gas expands and foams, thereby preparing foam particles; (2) the low boiling point liquid evaporation gasification foaming method, namely, the low boiling point liquid is pressed into polymer particles or under certain pressure and temperature conditions, so that the liquid is dissolved into the polymer particles, then the polymer is heated and softened, and the liquid is evaporated and gasified to foam, thereby preparing foam particles; (3) the supercritical foaming method is that other gases such as carbon dioxide, nitrogen and the like are injected into a special reaction device, under the conditions of certain pressure and temperature, the gases reach a supercritical state and are fully and uniformly mixed with polymer particles, then the pressure is relieved, or the particles to be foamed are led into a die cavity or an extrusion die to cause the sol to generate large pressure drop, so that the gases are separated out to form a large amount of bubble nuclei, and in the subsequent cooling forming process, the bubble nuclei in the sol continuously grow and are formed, and finally the microporous foam particles are obtained. (4) Dissolving out method, i.e. soaking liquid medium into polymer particles to dissolve out solid matter added in advance, so that a large amount of pores appear in the polymer particles to be in a foaming state, for example, mixing soluble matter salt and the like with the polymer, and after forming into a product, putting the product into water for repeated treatment, dissolving out the soluble matter, thus obtaining the open-cell foam particle product; (5) the method comprises the steps of adding hollow microspheres/expandable microspheres into a polymer, compounding, extruding for granulation, and performing thermal foaming to obtain closed-cell polymer foam particles; (6) a filling foamable particle method, namely mixing and filling foamable particles in a polymer, re-granulating, and then foaming the particles to be foamed to obtain the foam particle product; (7) the freeze-drying method is that polymer particles are swelled in a volatile solvent to be frozen, and then the solvent is escaped in a sublimation manner under the condition of approximate vacuum, thereby obtaining the porous sponge-shaped foam particle material.

The dilatant foam particles are prepared by preferably adopting an inert gas foaming method, a low-boiling-point liquid evaporation gasification foaming method and a supercritical foaming method. Wherein the inert gas and the low boiling point liquid are as described above with reference to the present invention.

In the present invention, when the polymer foam particles are directly prepared using a physical foaming method (more preferably, a supercritical foaming method), the foam particles may be prepared using an autoclave type foaming method or a continuous extrusion foaming method; the high-pressure kettle type foaming method comprises the steps of placing polymer particles and a physical foaming agent into a high-pressure reaction kettle, enabling the foaming agent to permeate/impregnate into the polymer particles at a certain temperature and under a certain pressure, keeping the temperature and the pressure for a period of time to enable the foaming agent to reach a saturated state in the polymer particles, then opening a pressure release valve to quickly release pressure, enabling a polymer particle/gas homogeneous phase system to generate thermodynamic imbalance, generating phase separation, nucleating and growing bubbles, and finally cooling and shaping to obtain polymer foam particles; the continuous extrusion foaming method is characterized in that a physical foaming agent (preferably supercritical fluid) is added into an extruder before or in the extrusion process, the physical foaming agent and a polymer component are melted and mixed uniformly in the extruder, the pressure of a melt flowing through a machine head is reduced, the foaming agent is volatilized to form a required foaming structure, materials can be granulated in the foaming process of the machine head to prepare foam particles, and the polymer foam particles are preferably obtained by adopting an underwater granulation mode. In addition, the present invention may also employ other foaming equipment suitable in the art to physically foam the polymer particles.

The supercritical foaming product has high specific strength and high cost performance, can greatly improve the dimensional precision of the product and shorten the development period of the product; the supercritical foaming method can greatly reduce the residual stress of the product, reduce and improve the buckling deformation of the product, eliminate surface sink marks, shorten the molding period of the thin-wall product, effectively save raw materials, reduce the product quality, and has the advantages of low viscosity, easy mold filling, simple equipment and process, low cost, environmental protection and the like, so the supercritical foaming method is used as an optimal preparation method of the polymer foam particles.

The chemical foaming method is a method for foaming particles to be foamed while generating gas along with chemical reaction in the foaming process, and includes, but is not limited to, the following methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) that causes the polymer particles to expand and foam. Among them, it is preferable to perform foaming by adding a chemical foaming agent to the polymer particles.

The 3D printing method comprises the steps of premixing an expandable polymer (composition) or an expandable polymer precursor (composition) with optional auxiliary agents and optional fillers by using an extruder, extruding and drawing the premix by using the extruder, using the premix for 3D printing, controlling a proper melting temperature, keeping the temperature for a certain time, spraying the premix through a nozzle of a printer, printing the premix into foam particles with a hole structure, and standing the foam particles in a constant-temperature oven for a period of time after printing to obtain the polymer foam particles.

In the preparation of the polymer foam particles, those skilled in the art can select a suitable foaming method to prepare the polymer foam particles according to the actual preparation situation and the target polymer properties.

In the present invention, the said skinned polymer foam particles have a skin structure, and the external shape of the foam particles can be selected from spherical, ellipsoidal, rice-shaped, cylindrical with hemispheres at both ends, egg-shaped, pie-shaped, polyhedral, irregular, etc., preferably spherical, ellipsoidal, polyhedral, etc. suitable for bonding/(surface) welding and filling; the resulting skinned polymeric foam particles preferably have a density of 0.01 to 1.0g/cm³More preferably 0.02 to 0.5g/cm³More preferably 0.05 to 0.2g/cm³(ii) a The Shore hardness of the prepared skin-carrying polymer foam particles is preferably 5-90A, and more preferably 5-60A; the average particle size of the prepared skin-carrying polymer foam particles is preferably 0.2-20mm, and more preferably 1-5 mm; the resulting skinned polymeric foam particles preferably have an average cell size of 10 to 100. mu.m. In the present invention, the skin structure means that the outer region of the foam particle has a non-porous or porous skin layer structure, which is different from the inner region (inner layer) structure; the structure includes physical structure (e.g., foam density, cell shape, hardness, foam gradient, etc.) and chemical structure. The particle surface of the foam particles of the present invention may be smooth or rough, and may be dense or non-dense; the inner layer and the skin layer of the foam particle can have the same foaming density or different foaming densities; the foaming density can gradually increase from the skin layer to the inner layer, can also gradually decrease, and can also present wavy change or other changes(ii) a change; the chemical structure of the different layers of the foam particles may also be completely different. The skin layer of the foam particles may have a higher density than the inner layer, thereby resulting in foam particles having better surface properties, and the skin layer of the foam particles may have a lower density than the inner layer, thereby resulting in foam particles having good resilience. In the invention, the skin layer density of the foam particle is preferably higher than that of the inner layer, and the density is gradually reduced from the skin layer to the inner layer, so that the foam particle has good and stable surface performance, and the skin-carrying foam particle is convenient to bond/weld. In the present invention, the surface structure, particularly the porous structure or the non-porous structure, of the skinned polymer foam particles can be controlled, thereby controlling the amount of the compounded dynamic polymer and other components penetrating into the polymer foam particles, thereby controlling the interfacial force between the foam particles and the dynamic polymer, even the interpenetrating network structure, and thus controlling the properties of the composite material and its products.

A preferred composite material is prepared by premixing the skinned polymer foam particles, the dynamic polymer or its raw materials, optional other auxiliary agents, and optional fillers, filling the mixture into a suitable mold, and hot-press molding the mixture under certain temperature and pressure conditions to obtain a composite material product.

A preferred composite material is prepared by premixing the skin-carrying polymer foam particles, the dynamic polymer or raw materials thereof, the foaming agent, optional other auxiliary agents and optional fillers, filling the mixture into a proper mold, and foaming the matrix under certain temperature and pressure conditions to prepare a matrix-foamed composite material product.

A preferred composite material is prepared by premixing the polymer particles to be foamed, the dynamic polymer or raw materials thereof, optional other auxiliary agents and optional fillers, filling the premixed material into a suitable mold, and foaming the polymer particles under certain temperature and pressure conditions to prepare a composite material product blended with the skin-carrying polymer foam particles.

A preferred composite material is prepared by premixing polymer particles to be foamed, dynamic polymer or raw materials thereof, foaming agent, optional other auxiliary agents and optional filler, filling the premixed mixture into a proper mold, and foaming the polymer particles and the matrix under certain temperature and pressure conditions to prepare a matrix-foamed composite material product.

Filling the premix into a proper mold, closing the mold, carrying out hot-press molding by using steam or hot air, stopping introducing the steam or hot air, removing the mold pressing, further expanding the composite sample until the composite sample is filled in the whole mold cavity, cooling, demolding and shaping to obtain a composite material product; wherein the mold clamping pressure is 0.1-15MPa, the mold temperature is 30-160 ℃, more preferably 60-100 ℃, the mold pressing time is 1-60min, more preferably 5-10min, and the specific parameters are determined according to the formula components and the performance of the required product; the cooling means used may be selected from water cooling, air cooling or other cooling means commonly used in the art. The molding method can prepare composite material products with the advantages of low density, low shrinkage degree, good appearance of molded bodies and the like, and has wide application range, so the molding method is a preferable preparation method of the invention.

In the invention, the premixing mode of the composite raw materials can be mixing in a batch, semi-continuous or continuous process mode; the mixing method includes, but is not limited to, mechanical stirring, kneading, banburying, and the like, the selected premixing method can be selected according to the form of the dynamic polymer (dynamic polymer raw material), if the dynamic polymer (dynamic polymer raw material) is solid powder or solid particles, the premixing can be performed by mechanical stirring, if the dynamic polymer (dynamic polymer raw material) is colloidal or elastomer, the premixing can be performed by kneading or banburying, wherein, in order to ensure the integrity of the skinned polymer foam particles in the mixing process, the temperature and the mixing rate should be controlled in the premixing process.

When the dynamic polymer or its raw material used has a low viscosity, the composite material can be prepared by filling the foam particles of the skinned polymer into a mold and then injecting the dynamic polymer or its raw material.

The invention also relates to a preparation method of the composite material, which comprises the steps of premixing the skinned polymer foam particles or the to-be-foamed polymer particles, the dynamic polymer or the raw materials thereof, optional other auxiliary agents and optional fillers, heating and melting by using an extrusion device, mixing a foaming agent before or in the extrusion process, melting and uniformly mixing the foaming agent and the polymer components, extruding the mixture from a machine head through a slit die orifice, and reducing the pressure of a melt flowing through the machine head to form a foaming structure to prepare the composite material product. The preparation method is suitable for the condition that the melting point of polymer (foam) particles is higher than that of dynamic polymer, and the dynamic polymer matrix is a thermoplastic matrix, especially the matrix is also foamed.

In the above preparation method, the foaming agent selected includes air, nitrogen, carbon dioxide, hydrocarbon, halogenated hydrocarbon, ether, ester, ketone, acetal, and suitable hollow microsphere/expandable microsphere, and the specific selection thereof can be referred to the above, and can also be selected from supercritical carbon dioxide, supercritical nitrogen, supercritical ethane, supercritical ethylene, supercritical propane, and the like. In the preparation method, the foaming agent is preferably supercritical carbon dioxide, supercritical nitrogen, hollow microspheres and expandable microspheres.

The invention also relates to a preparation method of the composite material, which comprises the steps of premixing the belt-skin polymer foam particles or the polymer particles to be foamed, the dynamic polymer or the raw materials thereof, optional other auxiliary agents and optional fillers, then adding the premixed materials into an extruder for melt plasticization, extruding the premixed materials from a head through a slit die orifice, and casting a molten material on a cooled steel material to prepare a composite material product. The preparation method is suitable for the condition that the melting point of polymer (foam) particles is higher than that of dynamic polymer, and the dynamic polymer matrix is a thermoplastic matrix.

The invention also relates to a preparation method of the composite material, which prepares the skinned polymer foam particles or the polymer particles to be foamed, the dynamic polymer or the raw materials thereof, the solvent, the optional other auxiliary agents and the optional fillers into a mixed solution with a certain concentration, then casts the mixed solution on continuously rotating steel at a certain speed, and prepares a composite material product by heating to remove the solvent and solidify the material. The preparation method is suitable for the condition that the dynamic polymer matrix has higher melting point but has good solvent.

In the present invention, the content of the components of the skinned polymer foam particles, the dynamic polymer, the blowing agent, the other auxiliaries and the filler in the composite material is not strictly limited.

Wherein the preferred weight ratio of blowing agent to polymer matrix is from 0.1 to 40 wt%, more preferably from 5 to 20 wt%; when present, the preferred weight ratio of the other adjuvants to the polymer matrix is from 0.1 to 10 wt%, more preferably from 0.5 to 2 wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30 wt%, more preferably from 5 to 20 wt%.

Wherein the preferred weight percentage of the skinned polymeric foam particles in the composite is 10-90 wt.%, more preferably 30-70 wt.%; the preferred weight proportion of the dynamic polymer in the composite is from 10 to 90 wt%, more preferably from 30 to 70 wt%; wherein, the weight part ratio of the skinned polymer foam particles to the dynamic polymer in the composite material is preferably 10: 90-90: 10, more preferably 30: 70-70: 30. Wherein, when the skin-carrying polymer foam particles in the composite material have a small specific gravity (the preferable weight proportion in the composite material is 10-30 wt%), a composite material is formed by taking the dynamic polymer as a continuous phase, the skin-carrying polymer foam particles are dispersed in a polymer matrix in a discontinuous phase in the form of islands and the like, and provide the composite material with rebound elasticity and energy absorption capability after molding and expansion, and the dynamic polymer as the continuous phase provides the composite material with dynamic reversible characteristics and good processability, wherein the dynamic polymer as the continuous phase can be selected to be crosslinked or not crosslinked according to the situation; when the dynamic polymer occupies a small proportion (the preferred weight proportion in the composite material is 10-30wt percent), the composite material taking the skin-bearing polymer foam particles as a continuous phase is formed, the dynamic polymer is distributed among the skin-bearing polymer foam particles in an interpenetration mode to provide dynamic characteristics for the composite material, and the foam particles as the continuous phase provide good rebound resilience and energy absorption capacity of the foam material for the composite material, wherein the skin-bearing polymer foam particles as the continuous phase can be selected to be crosslinked or not crosslinked according to the situation; when the arrangement and ratio of the skinned polymeric foam particles to the dynamic polymer in the composite are coincident (the ratio of parts by weight of the skinned polymeric foam particles to the dynamic polymer is preferably from 40: 60 to 60: 40, more preferably 50: 50), a bicontinuous phase composite can be formed, with the foam particle phase and the polymer phase being interdigitated, such that the composite has resilient, energy absorbing, and dynamic properties. In the preparation process of the composite material, when the dynamic polymer raw material is selected to prepare the composite material, the skinned polymer foam particles can be uniformly dispersed in the composite material due to the low viscosity of the composite material, so that the better distribution is obtained.

In a preferred composite formulation, the ratio of the foamed particles of the skinned polymer to the dynamic polymer is 70 to 100 wt% (wherein the ratio of the parts by weight of the foamed particles of the skinned polymer to the dynamic polymer is 10: 90 to 90: 10), the ratio of the foaming agent is 0 to 30 wt%, the ratio of the other auxiliary agents is 0 to 10 wt%, and the ratio of the filler is 0 to 30 wt%; in a more preferred composite formulation, the ratio of the foamed particles of the skinned polymer to the dynamic polymer is 70 to 84 wt% (wherein the ratio of the parts by weight of the foamed particles of the skinned polymer to the dynamic polymer is 30: 70 to 70: 30), the ratio of the blowing agent is 10 to 30 wt%, the ratio of the other auxiliary agents is 1 to 5 wt%, and the ratio of the filler is 5 to 20 wt%.

The dynamic polymer foam composite material has the dynamic characteristics of low density, light weight, heat insulation, sound insulation, buffering, shock absorption, self-repairing, recoverability and the like, so that the dynamic polymer foam composite material can be widely applied to manufacturing packaging materials, building materials, impact-resistant protective materials, shock absorption materials, buffering materials, noise reduction materials, heat preservation materials, shape memory materials, electronic and electrical materials, medical supplies and the like, and is particularly used for manufacturing products with energy absorption and dilatancy effects, such as foam components in helmet shells, human body protectors, shoe products, sports protective products, military police protective products, automobile bumpers, automobile upholstery, vehicle seats, buffering and shock absorption gaskets, fitness protective devices and ground covering materials. By adjusting the content and the foaming ratio of the foamed particles of the polymers with the skin in the composite material, the types, the distribution and the content of dynamic covalent bonds and supramolecular actions in dynamic polymers, the aggregation state structures of the foamed particles of the polymers with the skin and the dynamic polymers and other parameters, foamed products with different densities, rebound resilience, buffering property and dynamic property can be prepared.

In the application process of the dynamic components in the composite material, on one hand, mechanical energy can be lost through viscous flow, on the other hand, the difference of dynamic covalent bonds, the dynamic property of supermolecule action and the responsiveness in the polymer can be utilized, multiple absorption of energy can be achieved through reversible fracture, the multiple absorption of energy is mutually coordinated with the high resilience and the shock absorption and buffering property of the foam particles of the polymer with the skin, and the composite foam product with excellent energy absorption and buffering effects can be prepared through the combined action, so that the composite foam product has good damping, buffering, shock absorption, sound insulation, noise elimination, impact resistance and other effects. In addition, through proper component selection and formula design of the foam particle phase and the polymer phase, part of foam products can also show excellent shape memory performance, self-repairing performance, plastic deformation, bionic super toughness and the like, have incomparable excellent performance and can be widely applied to various fields.

Particularly, the composite material can be applied to the manufacture of damping shock absorbers for the vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and when the composite material is vibrated, foam particles and dynamic polymers in the composite material can dissipate a large amount of energy to play a damping effect, so that the vibration of a vibrator is effectively alleviated; the energy-absorbing buffering material with good plasticity, recoverability and reusability can be applied to the aspects of buffering packaging materials, sports protection products, impact protection products, military and police protection materials and the like, and the vibration and impact of objects or human bodies under the action of external force, including shock waves generated by explosion and the like, can be reduced; the energy-absorbing material with the shape memory function can be designed and applied to specific occasions, such as personalized and customized energy-absorbing protectors; the polymer foam board with the self-repairing function can be prepared, so that the material can self-heal internal or external damage, hidden dangers are eliminated, the service life of the material is prolonged, and the polymer foam board has the recoverable characteristic and the recycling capability. The prepared composite material with different matrixes and different structures (including a polymer structure, an aggregate structure and the like) can also be applied to different fields according to specific properties; for example, for thermoset matrix or high cross-linking degree composite materials, it is suitable for application in fields requiring high strength energy absorbing materials; for another example, for thermoplastic matrices or low glass transition temperature composites, which are suitable for energy absorbing applications in the areas of body protection, precision instruments, fragile objects, etc., for ease of fit/application. The composite material is particularly suitable for impact resistance protection of human bodies, animal bodies, articles and the like, for example, the material is used as a protective tool to protect the bodies in daily life, production and sports; the product can be made into other protective articles/appliances, and can be applied to the aspects of air-drop and air-drop protection, automobile anti-collision, impact resistance protection of electronic and electric appliances, and the like.

In addition, the composite material of the present invention can be applied to other various suitable fields according to the performance embodied therein, and those skilled in the art can expand and implement the composite material according to the actual needs.

Example 1

1, 6-hexamethylene diisocyanate and furfuryl alcohol are used as raw materials, dichloromethane is used as a solvent, stannous octoate is used as a catalyst, the molar ratio of the two is controlled to be 1: 2, the reaction is carried out for 2 hours at room temperature under the protection of nitrogen, and the reaction is carried out for 2 hours under reflux to prepare a difuran compound (a). Adding 1 molar equivalent of toluene-2, 4, 6-triyl triisocyanate into a three-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, adding DMF (dimethyl formamide) for dissolution and dilution, introducing argon for protection, then adding 1 molar equivalent of N-hydroxy maleimide and a small amount of butyl tin dilaurate solution, heating to 70 ℃ for reaction for 3h, and obtaining the diisocyanate containing maleimide groups. 2-formylphenylboronic acid and polyether amine with the molecular weight of about 1000 are used as raw materials, the molar ratio of the raw materials to the polyether amine is controlled to be 2: 1, the raw materials are dissolved in a toluene solvent, a proper amount of sodium borohydride is added as a reducing agent, and the aminomethyl phenylboronic acid end-capped polyether amine is synthesized through a Petasis reaction. Polyglycerol 500 and acrylic acid are used as raw materials to prepare double-bond terminated polyglycerol through esterification reaction, and then the double-bond terminated polyglycerol and 3-mercapto-1, 2-propylene glycol are subjected to mercaptan-olefin click addition reaction to prepare the 1, 2-glycol terminated polyglycerol.

Weighing 10g of aminomethyl phenylboronic acid terminated polyetheramine and 16g of 1, 2-diol terminated polyglycerol in a dry and clean reaction bottle, placing the mixture at 60 ℃ for continuously stirring and mixing, dripping a proper amount of triethylamine after mixing for 30min, heating to 80 ℃, continuing to react for 3h to obtain a borate polymer, and crushing the borate polymer into particles. Uniformly mixing 100g of borate polymer particles, 20g of hollow glass microspheres, 10.0mg of BHT antioxidant, 2g of silicon dioxide, 2g of antioxidant 4010NA and 1g of stearic acid, adding the mixture into a small internal mixer for mixing for 15min, adding the mixture into an extruder for extrusion blending, and carrying out underwater granulation on the obtained extruded sample strips at the extrusion temperature of 100-110 ℃ to obtain the skin-carrying polymer foam particles.

Weighing a certain amount of dichloromethane solvent in a dry clean flask, adding 4mmol of polyoxypropylene triol, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then slowly adding 6mmol of diisocyanate containing maleimide groups, reacting for 2h under the condition of 80 ℃ nitrogen protection, then cooling to 60 ℃, adding 4mmol of difuran compound (a), and continuing stirring for reacting for 1h to obtain a dynamic polymer sample.

Weighing 80 parts by weight of skinned polymer foam particles, 20 parts by weight of dynamic polymer samples, 20 parts by weight of gallium indium liquid alloy, 2 parts by weight of silicon dioxide, 0.02 part by weight of sodium dodecyl benzene sulfonate, 0.02 part by weight of bentonite, 0.02 part by weight of BHT antioxidant, 0.2 part by weight of antioxidant 4010NA and 1 part by weight of stearic acid, adding the materials into a screw extruder, controlling the head pressure to be 2Mpa and the extrusion temperature to be 130-140 ℃, continuously extruding to obtain a composite material, carrying out hot press molding in a proper mold, pressing the product (80 multiplied by 20mm) by hand to 75% of the thickness of the product, keeping the product for 60s, then slowly loosening, measuring the time required by the sample to restore to the deformation position with the initial thickness of 5%, recording the restoration time of the product by using a stopwatch to be 12.43s, wherein the composite material has good expansion fluidity and can disperse and absorb external energy through expansion flow effect, in addition, self-healing of the material can be achieved by heating. In this embodiment, can be applied to the electronic and electrical apparatus field as the shock-resistant protective material that has the heat conduction function with the combined material, in the in-process of using, can retrieve reuse to it for it has longer life.

Example 2

4-methyl-4-pentenoic acid and polymethylhydrosiloxane with the viscosity of about 3,000mPa & s are taken as raw materials, and silicon hydrogenation is carried out under the catalysis condition of a platinum-olefin complex Pt (dvs) to prepare the carboxylic acid modified siloxane. Allylamine and polymethylhydrosiloxane having a viscosity of about 3,000 mPas are used as raw materials, hydrosilylation is carried out under the catalysis of a platinum-olefin complex Pt (dvs) to prepare amino-modified siloxane, and the amino-modified siloxane is reacted in the presence of triethyl orthoacetate serving as a catalyst to obtain the amidino-modified siloxane. Reacting 6-bromo-1-hexene with excessive sodium azide to obtain 6-azido-1-hexene; 1 molar equivalent of propargyl acrylate and 1 molar equivalent of 6-azido-1-hexene were reacted in cyclohexanone at 90 ℃ for 3 hours to obtain the diolefin compound (a).

40ml of polymethylhydrosiloxane having a viscosity of about 3,000 mPas, 1.5g of diene compound (a), 1.2g of 1, 11-dibromoundecane, 2ml of a 1% Pt (dvs) -xylene solution as a catalyst were charged into a three-necked flask, heated to 80 ℃ and reacted for 24 hours under a nitrogen protection condition to obtain a polymer sample having a certain viscoelasticity, and the polymer sample was cut into particles having a suitable size. Weighing 100 parts by weight of polymer sample particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the polymer sample particles, adding 40 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, then heating the high-pressure reaction kettle to 110 ℃, keeping the pressure in the high-pressure kettle at 20bar, then maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, finally opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying.

0.02mol of amidino-modified siloxane and 0.02mol of carboxylic acid-modified siloxane were added to a dry and clean reaction flask, and the mixture was stirred at 80 ℃ for 5 hours to react, thereby obtaining a pale yellow and transparent dynamic polymer sample.

Weighing 40 parts by weight of polysiloxane foam particles, 60 parts by weight of a dynamic polymer sample, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, performing hot-press molding by using hot air, setting the mold temperature to be 90 ℃, the mold closing pressure to be 10Mpa and the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 0.81MPa, the elongation at break is 125%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 36%. In this example, the composite material produced can be used to produce foam gaskets that have good moldability and can be recycled for reuse.

Example 3

Adding 0.04mol of hydroxyl-terminated three-arm polyethylene oxide into a dry and clean reaction bottle, heating to 80 ℃, carrying out vacuum dehydration for 2h, adding 0.03mol of 1, 4-phenyl diboronic acid and a proper amount of triethylamine, stirring, mixing uniformly, heating to 80 ℃, reacting for 5h, preparing polyether-based polymer, and crushing the polyether-based polymer into particles. Weighing 90 parts by weight of polyether-based polymer particles, 10 parts by weight of foamable microspheres (Expancel microspheres from Acksonobel company), 0.08 part by weight of zinc borate, 8 parts by weight of sorbitan monolaurate and 0.05 part by weight of antioxidant 1010, uniformly mixing, adding into a double-screw extruder, controlling the pressure of a machine head to be 2Mpa, the extrusion temperature to be 160 ℃, controlling the water temperature of an underwater granulator to be 70 ℃, and carrying out underwater granulation to obtain the polyether foam particles.

0.04mol of polyoxypropylene triol, 0.02mol of dihydroxyamine compound (a) and 0.06mol of aldehyde-terminated polyethylene glycol 2,000 are added into a dry and clean reaction flask, and heated to 60 ℃ under the protection of nitrogen to react for 18h, so that a viscous dynamic polymer sample is obtained.

Weighing 40 parts by weight of polyether foam particles, 60 parts by weight of a dynamic polymer sample, 10 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, performing hot-air hot-press molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.12MPa, the elongation at break is 168%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 43%. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), the transmitted impact force is 15.24kN, and the composite material has good buffering and energy absorbing effects. The prepared composite material product can be used as an energy-absorbing protective material, has a protective effect on a base material, and can show different shock-absorbing and energy-absorbing effects along with the change of temperature and pH.

Example 4

5-hexenyl boric acid and 3- (allyloxy) -1, 2-propylene glycol are taken as raw materials, triethylamine is taken as a catalyst, and the boric acid ester compound (a) is prepared by condensation reaction at the temperature of 80 ℃.

Adding 5.6g of tetraisobutyl titanate and 30g of polydimethylsiloxane (with the molecular weight of 4000 and the viscosity of 1600 mPa.s at 25 ℃) into a dry and clean reaction bottle, adding a small amount of acetic acid aqueous solution, stirring and mixing for 30min, dropwise adding a small amount of BHT antioxidant, heating to 110 ℃, mixing and reacting for 4h to obtain modified polysiloxane, and crushing the modified polysiloxane into particles. Weighing 100 parts by weight of modified polysiloxane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the modified polysiloxane particles, adding 30 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 110 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying. A proper amount of dioctyl phthalate is measured, and PVC particles with the diameter of 0.5 mu m are added into the dioctyl phthalate, wherein the volume fraction of the PVC particles is 57%, so that the dilatant dispersion liquid is obtained. And pressurizing and soaking the prepared polysiloxane foam particles in the dilatant dispersion liquid for 2 hours, taking out the polysiloxane foam particles, wiping off residual liquid on the surface, and sintering the surface at a certain temperature to finally obtain the polysiloxane foam particles with dilatant properties.

40ml of polydimethylsiloxane with the viscosity of about 1000 mPas, 15g of ethylene-vinyl acetate copolymer, 0.8g of triallyl isocyanurate, 2.4g of borate compound (a) and 2g of silane coupling agent KH550 are added into a reactor and uniformly mixed, and the mixture is placed in an ultraviolet radiation crosslinking device and irradiated by ultraviolet light for 30min to obtain the hybrid crosslinked dynamic polymer.

Weighing 40 parts by weight of polysiloxane foam particles with dilatancy, 60 parts by weight of hybrid cross-linked dynamic polymer, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA, 2 parts by weight of silane coupling agent KH550 and 1 part by weight of stearic acid, adding the materials into a small internal mixer, mixing for 15min, filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature at 90 ℃, the mold closing pressure at 5MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material, and detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.56MPa, the elongation at break is 435%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 50%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as a recovery time of 5.80s with a stopwatch. The composite material can keep elasticity in a normal state, shows temporary rigidity when being impacted, and returns to a normal elastic state after being impacted, and the prepared composite material can be used for manufacturing a functional buffer gasket with a viscosity-elasticity conversion effect for damping of electronic and electric appliances.

Example 5

Taking methyl mercapto siloxane with molecular weight of about 60,000 and dimethyl dithio-amino-formic allyl ester as raw materials, taking DMPA as a photoinitiator, and preparing mercapto siloxane (a) containing disulfide ester side groups by thiol-ene click reaction under the condition of ultraviolet irradiation. The diene double-end-capped siloxane is prepared by using hexadienol and hydroxyl-terminated siloxane with the molecular weight of about 500 as raw materials, controlling the molar ratio of the hexadienol and the hydroxyl-terminated siloxane to be 2: 1 and performing hydrolytic condensation.

Adding 3.8g of boric acid into a reaction bottle, adding 50ml of polydimethylsiloxane (molecular weight of 2000 and viscosity of 1200mPa & s at 25 ℃), adding a proper amount of triethylamine, heating to 80 ℃ and reacting for 2 hours to obtain the modified polysiloxane particles. Weighing 100 parts by weight of modified polysiloxane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the modified polysiloxane particles, adding 30 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 110 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying. Weighing a proper amount of deionized water, and adding corn starch microparticles into the deionized water, wherein the volume fraction of the corn starch microparticles is 40%, so as to obtain the dilatant dispersion liquid. And pressurizing and soaking the prepared polysiloxane foam particles in the dilatant dispersion liquid for 2 hours, taking out the polysiloxane foam particles, wiping off residual liquid on the surface, and sintering the surface at a certain temperature to finally obtain the polysiloxane foam particles with dilatant properties.

Adding 200ml of THF (tetrahydrofuran), then adding 15g of mercaptosiloxane (a) containing disulfide ester side groups, 3.86g of diene double-end siloxane and a proper amount of zinc chloride serving as a catalyst, heating to 50 ℃, stirring and dissolving, then adding 1.2g of tetramethylammonium hydroxide and 0.8g of sodium glycerol, continuing to react for 2h, then continuing to stir and react for 24h at 50 ℃, and then placing the sample in a vacuum oven at 50 ℃ to obtain polysiloxane colloid with certain viscoelasticity.

Weighing 50 parts by weight of polysiloxane foam particles with dilatancy, 50 parts by weight of polysiloxane colloid, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, then filling the premix into a proper mold, closing the mold, carrying out hot-press molding by using hot air, setting the mold temperature at 90 ℃, the mold closing pressure at 5Mpa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material, wherein the surface of the composite material is soft, and products with different appearance sizes can be manufactured according to the shape of the mold. The tensile strength and elongation at break of the samples were measured according to DIN EN ISO 1856 (where the test rate was 100mm/min), the tensile strength of the samples was 2.28MPa and the elongation at break was 265%, and the resilience of the samples was measured according to DIN53512 and was 41%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as a recovery time of 13.50s with a stopwatch. The composite material was subjected to an impact test according to EN1621-2012 standard (sample thickness 10mm, test height 50cm), and the transmitted impact force was found to be 17.54kN, with a certain cushioning capacity. In addition, the composite material exhibits flexibility and good compressibility at low compression rates, but at high compression rates, the material modulus increases, exhibiting dilatancy; the fractured sample is placed in a 60 ℃ mould under stress at the fracture surface or the fracture surface can be bonded again after being irradiated by ultraviolet light with certain wavelength, and the sample has self-repairing property and recyclability. In the embodiment, the composite material sample can be used as a personalized, customized and recyclable energy absorption pad, and has good self-repairing capability and energy absorption effect.

Example 6

Mixing ethanedithiol and 3-chloro-2-chloromethyl-1-propene at a molar ratio of 2: 1 by using methanol as a solvent and sodium methoxide as a catalyst, and reacting for 16h under a heating condition to obtain a dithiol compound (a). DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercaptopropionic acid and 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare carboxyl graft modified polybutadiene. The amino graft modified polybutadiene is prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on mercaptoethylamine and 1, 3-polybutadiene.

Weighing 40g of styrene butadiene rubber, 30g of carboxyl graft modified polybutadiene, 30g of amino graft modified polybutadiene, 20g of hollow glass microspheres, 10mg of BHT antioxidant, 15g of carbon black, 0.5g of benzoyl peroxide and 1.5g of antioxidant 4010NA, uniformly mixing, adding into a small internal mixer, mixing for 20min, adding into an extruder, extruding and blending at the extrusion temperature of 110-120 ℃, granulating the obtained extruded sample strips to obtain rubber foam particles, and preparing the rubber foam particles into a rubber foam particle sheet by hot press molding.

30g of nitrile rubber (b) is weighed and added into a small internal mixer for mixing for 20min, 1.2g of dithiol compound (a), 0.12g of photoinitiator DMPA, 0.08g of ruthenium-based catalyst 1, 1.5g of zinc stearate, 1.5g of tribasic lead sulfate, 4g of carbon black, 0.05g of barium stearate, 0.2g of anhydrous sodium sulfate, 0.1g of antioxidant 168 and 0.2g of antioxidant 1010 are added, and the mixture is heated to 80 ℃ and continuously mixed for 20 min. Taking out the mixed materials, cooling, placing in a double-roller machine, pressing into slices, cooling at room temperature, cutting into pieces, taking out the prepared polymer slices, reacting for 15min under ultraviolet irradiation, placing in a vacuum oven at 80 ℃ for 4h for further reaction and drying, cooling to room temperature, and placing for 30min to obtain the nitrile rubber sheet.

Weighing a proper amount of rubber foam particle sheets and nitrile rubber sheets, adhering the rubber foam particle sheets and the nitrile rubber sheets in a layer-by-layer alternating mode through an adhesive to prepare a composite material with a multilayer composite structure, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental speed is 100mm/min), the tensile strength of the sample is 5.80MPa, the elongation at break is 135%, detecting the rebound resilience of the sample according to DIN53512 standard, and the rebound resilience is 46%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as 8.76s by means of a stopwatch. The obtained composite material has good flexibility and tensile toughness, can dissipate stress through self deformation and dilatancy effect, and can be made into an antistatic impact-resistant protective foam pad for use.

Example 7

4- (4-iodine-2, 3, 5, 6-tetrafluorophenoxy) butyl-1-alcohol and 4-pentenoyl chloride react under the catalysis of triethylamine to obtain an alkene-containing compound (b) with halogenated phenyl. And (c) reacting 4-pentenoyl chloride and 6-hydroxymethyl quinoline in equal molar equivalents under the catalysis of triethylamine to obtain the quinoline compound (c) with one end being an alkenyl group.

50g of methylhydrogen-containing siloxane (molecular weight: about 30,000) was charged in a dry clean three-necked flask, and after 1 hour of introduction of nitrogen, 8.4g of tetraphenyldiolefin compound (b), 1.14g of 4-methyl-4-pentenoic acid, and 0.5g of ZnCl were added₂2ml of 1 percent Pt (dvs) -xylene solution is used as a catalyst, the temperature is heated to 80 ℃, the reaction is continued for 24 hours under the protection of nitrogen, and finally the soft surface and certain toughness are obtainedA force responsive polymer. Weighing 100g of force-responsive polymer sample, 10mg of BHT antioxidant, 15g of light calcium carbonate and 1.5g of antioxidant 4010NA, uniformly mixing, adding the mixture into a small internal mixer for mixing for 20min, then adding the mixture into an extruder for extrusion and wire drawing, wherein the extrusion temperature is 110-120 ℃, printing the obtained wire sample by using a 3D printer, controlling the melting temperature of the equipment to be 100 ℃, keeping the temperature for 15min, then spraying the wire sample by using a nozzle of the printer, printing the wire sample into foam particles with holes and an outer skin structure, after the printing is finished, placing the foam particles in a constant-temperature oven for standing for a period of time, and taking out the foam particles and naturally cooling to obtain the force-responsive polysiloxane foam particles.

50ml of methyl hydrogen-containing siloxane (molecular weight: about 20,000) was charged into a dry clean three-necked flask, and after 1 hour of nitrogen gas introduction, 1.1g of 1, 7-octadiene, 3.2g of an ene-containing compound (b) having a halogenated phenyl group, 2.2g of a quinoline compound (c) having an alkenyl group at one end, and 2ml of a 1% Pt (dvs) -xylene solution as a catalyst were heated to 80 ℃ and reacted further for 24 hours under a nitrogen gas protection condition to obtain a dynamic polymer colloid.

Weighing 40 parts by weight of force-responsive polysiloxane foam particles, 60 parts by weight of dynamic polymer colloid, 2 parts by weight of silicon dioxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material, detecting the tensile strength and the elongation at break of a sample according to DIN ENISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 1.09MPa, the elongation at break is 212%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 41%. The buffer layer can be used as an intermediate buffer layer of electronic and electrical equipment or precision instruments with a powerful color development effect, and plays a role in protecting the equipment.

Example 8

And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polyethylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polyethylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10.

Isopropyl boric acid and 3-aminopropyl dimethyl methoxy silane are used as raw materials, tetrahydrofuran is used as a solvent, the molar ratio of the isopropyl boric acid to the tetrahydrofuran is controlled to be 1: 2, and a diamino compound (a) is obtained through condensation reaction at the temperature of 60 ℃.

Uniformly mixing 80 parts by weight of polyethylene, 3 parts by weight of talcum powder, 1.5 parts by weight of coupling agent, 0.8 part by weight of zinc oxide, 1 part by weight of zinc stearate, 3 parts by weight of polyethylene wax and 0.05 part by weight of antioxidant 1010, adding the mixture into an extruder for extrusion and wire drawing, wherein the extrusion temperature is 150-170 ℃, printing the obtained silk sample by using a 3D printer, controlling the melting temperature of equipment to be 150 ℃, keeping the temperature for 15min, then spraying out the silk sample through a nozzle of a printer, printing the silk sample into foam particles with holes and an outer skin structure, placing the silk sample into a constant-temperature oven for standing for a period of time after printing, taking out and naturally cooling to obtain the polyethylene foam particles.

25g of maleic anhydride grafted polyethylene, 1.8g of diamino compound (a), 2.4g of 8-hydroxybenzo [ a ] pyrene, 2.0g of ethyl- (3-hydroxypropyl) -dimethylammonium and 10mg of BHT antioxidant are added into a dry and clean three-neck flask, heated to 160 ℃ under the protection of nitrogen, melted, stirred and mixed for 1h, then 0.35g of p-toluenesulfonic acid, 3.0g of plasticizer DOP and 0.5g of simethicone are added, and the reaction is continued for 3h under the protection of nitrogen. Then pouring the mixture into a proper mould, carrying out compression molding by using a molding press at the temperature of 120 ℃, then cooling to room temperature and standing for 30min to finally obtain a polyethylene-based polymer sample, and cutting the polyethylene-based polymer sample into granules with uniform size.

Weighing 30 parts by weight of polyethylene foam particles and 70 parts by weight of polyethylene polymer particles, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of adhesive, closing the mold, setting the mold temperature at 130 ℃, the mold closing pressure at 15Mpa, the mold pressing time at 15min, then releasing the pressure, cooling and demolding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), detecting the tensile strength of the sample at 9.82MPa, and the elongation at break at 142%, detecting the rebound resilience of the sample according to DIN53512 standard, wherein the rebound resilience is 58%, and the composite material product has good resilience. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), and the transmitted impact force is measured to be 15.08kN, so that the composite material has a good shock absorption and buffering effect. In the embodiment, the prepared composite material can be used for manufacturing automobile anti-seismic buffer systems, sports protector materials and the like.

Example 9

Weighing 90 parts by weight of polystyrene particles (412B, Beijing Yanshan petrochemical company), 3 parts by weight of silicon dioxide, 1 part by weight of talcum powder and 0.05 part by weight of antioxidant 168, adding the materials into a screw extruder, uniformly mixing, extruding and granulating to obtain the polystyrene particles suitable for foaming. Then weighing 100 parts by weight of polystyrene particles, 300 parts by weight of absolute ethyl alcohol/benzene mixed solvent and 7 parts by weight of magnesium pyrophosphate, adding the weighed materials into a high-pressure reaction kettle, injecting 40 parts by weight of butane under a stirring state, then heating the high-pressure reaction kettle to 130 ℃, keeping the pressure in the high-pressure reaction kettle at 20bar, then maintaining the temperature and the pressure for 2 hours, finally opening a discharge valve at the bottom end of the high-pressure reaction kettle, taking out the foam particles, washing and air-drying.

Weighing 25g of styrene-maleic anhydride copolymer, 2.0g of N-aminoethyl-S-aminoethyl dithiocarbamate (a), 2.3g of 2-hydroxymethylpyrene (b), 0.16g of p-toluenesulfonic acid, 0.8g of tribasic lead sulfate, 0.4g of di-N-butyltin dilaurate, 3g of dioctyl phthalate, 0.2g of stearic acid, 0.02g of antioxidant 168 and 0.04g of antioxidant 1010, uniformly mixing, adding the mixture into an extruder for extrusion and wire drawing, wherein the extrusion temperature is 120-130 ℃, printing the obtained silk sample by using a 3D printer, controlling the melting temperature of equipment to be 110 ℃, keeping at the temperature for 15min, spraying via a nozzle of a printer, printing into foam particles with holes and outer skin structure, after printing, and standing in a constant-temperature oven for a period of time, taking out and naturally cooling to obtain the polystyrene foam particles.

Weighing 70 parts by weight of polystyrene foam particles and 30 parts by weight of styrene-based dynamic polymer particles, premixing by using a stirrer, then filling the premix into a proper mould, adding a proper amount of adhesive, closing the mould, setting the mould temperature at 120 ℃, the mould closing pressure at 15Mpa and the mould pressing time at 15min, then releasing the pressure, cooling and demoulding to obtain a composite material product, the surface of the polystyrene foam product is smooth, the polystyrene foam product has certain glossiness and certain hardness and mechanical strength, the tensile strength and the elongation at break of a sample are detected according to DIN EN ISO 1856 standard (wherein the experimental speed is 100mm/min), the tensile strength of the sample is 5.27MPa, the elongation at break is 185%, and compared with the tensile strength (0.15MPa) and the elongation at break (100%) of a traditional polystyrene foam product, the polystyrene foam product has more excellent mechanical strength and toughness. The prepared composite material can be used as a foam outer packaging material, and plays roles of heat preservation and buffering for internal articles.

Example 10

DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercapto-1, 2, 4-triazole and polyisoprene are subjected to thiol-ene click reaction to prepare the azole graft modified polyisoprene. Taking DMPA as a photoinitiator and ultraviolet light as a light source, and carrying out thiol-ene click reaction on 12-mercapto dodecyl phosphoric acid and polyisoprene to prepare the phosphoric acid grafted modified polyisoprene.

Uniformly mixing 100g of polyisoprene rubber, 20g of force-responsive filler (a), 10mg of BHT antioxidant, 2g of foaming agent AC, 2.5g of zinc oxide, 1g of dicumyl peroxide and 1.5g of anti-aging agent 4010NA, adding the mixture into a small internal mixer, mixing for 20min, adding the mixture into an extruder, extruding and drawing wires at the extrusion temperature of 110-120 ℃, printing the obtained wire sample by using a 3D printer, controlling the melting temperature of the device to be 100 ℃, keeping the temperature for 15min, then spraying the wire sample by using a nozzle of the printer, printing the wire sample into foam particles with holes and an outer skin structure, placing the foam particles into a constant-temperature oven after printing, standing for a period of time, and taking out the foam particles naturally cooled to obtain the force-responsive foam rubber particles.

Weighing 22g of azole grafted modified polyisoprene, 20g of phosphoric acid grafted modified polyisoprene, 0.05g of ruthenium-based catalyst 2, 0.24g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010, uniformly mixing, adding into a small internal mixer for banburying and blending, taking out a sample after mixing, putting into a compression mold, closing the mold, pressurizing and heating at the mold pressing temperature of 100-110 ℃, the mold pressing time of 15-20min and the pressure of 10MPa, taking out, cooling to room temperature, and standing for 30min to finally obtain the polymer rubber.

Weighing 50 parts by weight of force-responsive foam rubber particles, 50 parts by weight of polymer rubber, 8g of conductive graphite, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, hot air hot-pressing for molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material, wherein the composite material has good rebound resilience, and can be quickly rebounded by pressing the composite material with fingers. The samples were tested for their resilience according to DIN53512 and had a resilience of 50%. In the embodiment, the composite material sample can be made into a conductive buffer material for use, and external acting force can be sensed and monitored by measuring the conductivity and fluorescence effect of the material under the action of stress.

Example 11

Adding a certain amount of polycarbonate diol (with the molecular weight of about 2,000) into a dry and clean reaction bottle, dropwise adding a small amount of triethylamine under the ice bath condition, continuously stirring, then dropwise adding a certain amount of dichloromethane solution dissolved with cinnamoyl chloride, and continuously stirring under the ice bath condition for reaction to obtain the cinnamate double-ended polycarbonate (a), wherein the molar ratio of the polycarbonate diol to the cinnamoyl chloride is 1: 2. Under the condition of anhydrous vacuum pumping at 90 ℃, dissolving limonene oxide and a catalyst (b) in toluene, keeping the molar ratio of the limonene oxide to the catalyst at 50: 1, introducing 10bar of carbon dioxide into a reaction container, and after the reaction is completed, precipitating a crude product with methanol to obtain a poly-limonene carbonate chain segment. The resulting poly (limonene carbonate) segments and 1, 3-propanediol were dissolved in toluene, and 1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, catalyst, was added to react at 80 ℃ for 3 hours to obtain poly (limonene carbonate) (c) having an average molecular weight of about 2,000 and both ends terminated with hydroxyl groups.

10 molar equivalents of the poly (limonene carbonate) (c) and 1 molar equivalent of 1, 6-hexanedithiol were dissolved in tetrahydrofuran and thoroughly blended, and reacted in the presence of a photoinitiator BDK under irradiation of an ultraviolet lamp to prepare a polymer 1. 70 parts by weight of polymer 1, 10 parts by weight of spiropyran crystals, 0.3 part by weight of talcum powder and 0.05 part by weight of antioxidant 1010 are uniformly mixed, and then the mixture is added into a screw extruder to be granulated to obtain force-responsive carbonate particles suitable for foaming. Then weighing 100 parts by weight of force-responsive carbonate particles, 400 parts by weight of water and 7 parts by weight of tricalcium phosphate, adding the materials into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide under the stirring state, then heating the high-pressure reaction kettle to 116 ℃, keeping the pressure in the high-pressure kettle at 20bar, then maintaining the temperature and the pressure for 2 hours, finally opening a discharge valve at the bottom end of the high-pressure kettle, taking out the foam particles, washing and air-drying.

Weighing 30g of polycarbonate (a) double-ended with cinnamate, 3.0g of diphenyl carbonate and 0.09g of zinc acetate in a dry and clean reaction bottle, reacting for 2h under the protection of nitrogen at 80 ℃, cooling to room temperature after the reaction is finished, irradiating for 30min under 280nm ultraviolet light to obtain modified polycarbonate, and cutting the modified polycarbonate into particles with uniform size.

Weighing 30 parts by weight of force-responsive carbonate foam particles and 70 parts by weight of modified polycarbonate particles, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of adhesive, closing the mold, setting the temperature of the mold to be 110 ℃, the closing pressure to be 5Mpa, the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain a composite material product, wherein the composite material can show different fluorescence effects under different stress or illumination conditions, can be used for manufacturing a stress indicating material, and warns by fluorescence change when the stress of the composite material exceeds a certain load.

Example 12

The amino compound (a) is obtained by condensation reaction at 60 ℃ by using equimolar amounts of 2-aminoethylaminoboronic acid and dopamine as raw materials and tetrahydrofuran as a solvent. Adding 1 molar equivalent of toluene-2, 4, 6-triyl triisocyanate into a three-neck flask, dehydrating in vacuum at 120 ℃ for 2h, adding DMF (dimethyl formamide) for dissolving and diluting, introducing argon for protection, then adding 1 molar equivalent of ligand compound (b) and a small amount of butyl tin dilaurate ethyl ester solution, heating to 70 ℃ for reaction for 3h, and obtaining the diisocyanate containing the metal palladium ligand.

100 parts by weight of thermoplastic polyurethane particles (685A, BASF, Germany), 400 parts by weight of water and 7 parts by weight of tricalcium phosphate are added into an autoclave, 40 parts by weight of supercritical carbon dioxide is injected under the stirring state, then the autoclave is heated to 116 ℃, the pressure in the autoclave is kept at 20bar, then the autoclave is maintained for 2 hours under the conditions of temperature and pressure, and finally a discharge valve at the bottom end of the autoclave is opened, and the foam particles are taken out, washed and dried in the air.

Weighing 30g of polyurethane foam particles, 20g of polyethylene glycol 400, 1.6g of amino compound (a), 2.4g N, N-dihydroxy-4-pyridylamine, mixing and stirring uniformly, adding 8.4g of diisocyanate containing a metallic palladium ligand, heating to 60 ℃, reacting for 3h in a nitrogen atmosphere, adding 2.4g of metallic osmium heteroaromatic ring particles, 1.6g of nano-silver particles and 0.01g of bentonite, filling into a proper mold, closing the mold, setting the mold temperature to be 90 ℃, the mold closing pressure to be 10MPa, the mold pressing time to be 10min, releasing the pressure, cooling and demolding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.54MPa, the elongation at break is 231%, compared with the traditional polyurethane foam with similar tensile strength, the elastic modulus of the steel has a remarkable improvement (20% → 231%) in elongation at break, and shows excellent toughness, and the elastic modulus of the steel is 42% when the sample is tested according to DIN 53512. By utilizing the dynamic characteristic and good toughness of the composite material, the composite material can be made into an impact-resistant gasket with heat conduction characteristic, and the impact-resistant gasket can be applied to the field of electronic and electric appliances and can be repaired by heating when the impact-resistant gasket is damaged.

Example 13

Equimolar toluene-2, 4, 6-triyl triisocyanate and 4-hydroxymethyl-tetrathiafulvalene are reacted to prepare tetrathiafulvalene modified diisocyanate.

100 parts by weight of thermoplastic polyurethane particles (1170A, BASF in Germany), 400 parts by weight of water and 7 parts by weight of tricalcium phosphate are added into a high-pressure reaction kettle, 40 parts by weight of supercritical carbon dioxide is injected under the stirring state, then the high-pressure reaction kettle is heated to 116 ℃, the pressure in the high-pressure reaction kettle is kept at 20bar, then the high-pressure reaction kettle is maintained for 2 hours under the conditions of temperature and pressure, finally, a discharge valve at the bottom end of the high-pressure reaction kettle is opened, and the foam particles are taken out, washed and air-dried.

Adding 10g of bisphenol A polyoxyethylene ether (a), 1.74g of dinitrocarbene compound (b), 0.58g of N, N' -di-tert-butyl hexamethylene diamine (c), 1.5g of dibutyltin dilaurate and 0.8g of organic silicone oil into a reactor, mixing and stirring uniformly at room temperature, adding 11.5g of tetrathiafulvalene modified diisocyanate, reacting for 1h under the protection of nitrogen, adding 2 wt% of silicon dioxide and 0.3 wt% of sodium dodecyl benzene sulfonate, and continuing to react for 2h after ultrasonic treatment for 20 min. After the reaction is finished, pouring the polymer solution into a proper mould, placing the mould in a vacuum oven at 80 ℃ for 12h for further reaction, cooling to room temperature, and placing for 30min to finally obtain a dynamic polyurethane sample.

Weighing 20 parts by weight of polyurethane foam particles, 80 parts by weight of a dynamic polyurethane sample, 20 parts by weight of gallium-indium liquid alloy, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature to be 110 ℃, the closing pressure to be 10MPa, the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain the composite heat conduction material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 1.98MPa, the elongation at break is 223%, and compared with the traditional polyurethane foam with similar tensile strength, the elongation at break is remarkably improved (20% → 223, the elastic modulus of the sample is detected according to DIN53512 standard, the elastic modulus is 52%, and the elastic modulus has good elastic modulus.

Example 14

Adding 60 parts by weight of polyether KGF700, 20 parts by weight of polyether KGF3010, 5 parts by weight of tetrahydroxy compound (c) and 0.5 part by weight of polyurethane catalyst A-1 and 1 part by weight of silicone oil into a dry and clean reaction bottle, and uniformly mixing and stirring to obtain a material A; weighing 40 parts by weight of triphenylmethane triisocyanate, quickly mixing with the material A, quickly stirring and reacting by using a special stirrer, pouring into a proper mold, keeping the mold temperature at 56 ℃, opening the mold after 7min to obtain a polyurethane sample, cutting the polyurethane sample into polyurethane particles with proper size, then adding the polyurethane particles into an extruder for extrusion and wire drawing, wherein the extrusion temperature is 150-.

Adding 0.03mol of polycaprolactone diol with the molecular weight of about 1,000 and 0.02mol of hydroxyethyl hexahydro-s-triazine (b) into a dry and clean reaction bottle, dropwise adding a small amount of triethylamine, uniformly mixing, adding 0.04mol of hexamethylene diisocyanate trimer, reacting for 3 hours in a nitrogen atmosphere, and obtaining the dynamic polyurethane elastomer with good resilience after the reaction is finished.

Weighing 60 parts by weight of polyurethane foam particles, 40 parts by weight of dynamic polyurethane elastomer, 10 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, performing hot-air hot-press molding, setting the mold temperature at 110 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.52MPa, the elongation at break is 242%, compared with the traditional polyurethane foam with similar tensile strength, the elongation at break is remarkably improved (20% → 242%), detecting the rebound rate of the sample according to DIN53512 standard, the rebound resilience was 42%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as 8.64s by a stopwatch. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), the transmitted impact force is measured to be 12.06kN, and the composite material has a good buffering and energy absorbing effect. The obtained composite material has good dilatancy and energy-absorbing characteristics, the material does not generate color change at low impact rate, but can generate color change at high impact rate, and embodies the dilatancy to disperse and absorb external energy, the material can be used as an energy-absorbing buffer gasket for damping and silencing of precise instruments or electronic products, can show different buffering and damping effects at different temperatures, and can realize self-repairing of the material by illumination or heating.

Example 15

The boric acid ester compound (c) is obtained by condensation reaction of 2-aminomethyl phenylboronic acid and 2- (4-aminobutyl) propane-1, 3-diol which are equal molar weight as raw materials and tetrahydrofuran as a solvent at the temperature of 60 ℃.

200ml of chloroform, 10g of polyoxypropylene triol, 1.5g of a carboxylic acid compound (a), 0.8g of 1, 6-adipic acid, 3.8g of dicyclohexylcarbodiimide condensing agent and 0.5g of a catalyst, namely 4-dimethylaminopyridine are weighed in a dry clean flask, uniformly mixed and reacted for 6 hours at 80 ℃, 2.20g of a dithioester derivative (b) is added, the mixture is uniformly stirred and mixed and then reacted for 2 hours, the viscous reaction solution is poured into a proper mould and placed in a vacuum oven at 80 ℃ for 24 hours for further reaction, then the reaction solution is cooled to room temperature and placed for 30 minutes, and finally a polymer sample is obtained and cut into particles with proper size. Weighing 100 parts by weight of polymer sample particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the polymer sample particles, adding 40 parts by weight of supercritical carbon dioxide into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 118 ℃, keeping the pressure in the high-pressure reaction kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, finally opening a discharge valve at the bottom end of the high-pressure reaction kettle, taking out foam particles, washing and air-drying the foam particles, and preparing the foam particles into a foam particle sheet by means of hot press molding.

Adding 80ml of THF solvent into a dry and clean reaction bottle, introducing nitrogen to remove oxygen for 1h, adding 9g of polyethylene glycol 400, 2.4g of boric acid ester compound (c), 4.4g of benzoyl compound (d) and 8.4g of 1, 6-hexamethylene diisocyanate, carrying out reflux reaction for 3h, pouring the mixture into a proper mold, placing the mold in a vacuum oven at 80 ℃ for 12h for further reaction, and obtaining the dynamic polyurethane elastomer with good resilience after the reaction is finished.

Weighing 80 parts by weight of polymer foam particles, 20 parts by weight of dynamic polyurethane elastomer, 10 parts by weight of gallium-indium liquid alloy, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer, mixing for 10min, filling the premix into a proper mold, closing the mold, hot air hot-pressing for molding, setting the mold temperature at 110 ℃, the mold closing pressure at 10MPa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material, wherein the prepared composite material has excellent resilience, can be molded into a temporary shape under the action of external force, rapidly releases stress after being stretched at a high speed by using the external force, can recover the original shape, and shows a shape memory function, and in addition, the dynamic polymer contained in the composite material enables the composite material to have a certain self-repairing capability, the material can be used as a shape memory damping material to be applied to automobile parts, and plays a role in reducing noise and vibration.

Example 16

Adding 15g of 2, 4-di-tert-butylphenol, 10g of 4-hydroxymandelic acid and 30ml of acetic acid into a reaction bottle, heating to 95 ℃, uniformly mixing, adding 0.09ml of methanesulfonic acid, continuing to react for 3h, cooling overnight, filtering and purifying to obtain an intermediate product 1, dissolving the intermediate product 1 in an NaOH aqueous solution, heating to 80 ℃ under the protection of nitrogen, adding a proper amount of 3-chloro-1, 2-propanediol, continuing to react for 3h, cooling to room temperature, adding a hydrochloric acid aqueous solution, heating to 80 ℃, continuing to react for 1h, purifying to obtain an intermediate product 2, uniformly mixing the intermediate product 2 with di-tert-butyl peroxide and benzene, irradiating by ultraviolet light at 30 ℃ for 90min, and purifying to obtain a compound (a).

100g of thermoplastic polyurethane particles (5377, Germany Bayer), 20g of hollow glass microspheres, 10g of dye molecule type force-responsive filler (b), 10.0mg of BHT antioxidant, 2g of silicon dioxide, 6g of stearic acid, 10g of graphene and 5g of anti-aging agent are uniformly mixed, added into a small internal mixer for mixing for 15min, then added into an extruder for extrusion blending, the extrusion temperature is 120-130 ℃, and the obtained extruded sample strips are granulated to obtain the force-responsive polyurethane foam particles.

200ml of toluene solvent is weighed in a reaction bottle, 25g of polycarbonate diol with the molecular weight of about 2,000, 2.5g of diphenyl carbonate, 0.06g of zinc acetate and 4.78g of compound (a) are added, the mixture is stirred and mixed uniformly, heated to 80 ℃ and dehydrated in vacuum for 1h, 12g of diphenylmethane diisocyanate is added, the mixture is reacted for 6h under the protection of nitrogen at 80 ℃, and after the reaction is finished, the mixture is cooled to room temperature, and the prepared dynamic polymer elastomer is cut into particles with uniform size.

Weighing 70 parts by weight of force-responsive polyurethane foam particles and 30 parts by weight of dynamic polymer elastomer particles, premixing by using a stirrer, then filling the premix into a proper mould, adding a proper amount of polyurethane adhesive, closing the mould, setting the temperature of the mould to be 90 ℃, the closing pressure to be 5Mpa and the mould pressing time to be 10min, then releasing the pressure, cooling and demoulding to obtain a composite product, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental speed is 100mm/min), the tensile strength of the sample is 2.95MPa, the elongation at break is 308 percent, compared with the traditional polyurethane foam with similar tensile strength, the elongation at break of the material is remarkably improved (20% → 308%), and the rebound resilience of the sample is 46% according to DIN 53512. The prepared composite material can realize force-induced fluorescence under the action of mechanical force, can be applied to automobile parts as a damping material with a stress monitoring function, and plays roles in reducing noise and vibration.

Example 17

Adding 18.2mL of 4-methoxybenzaldehyde into a flask, slowly dropwise adding 120mL of an aqueous solution dissolved with 34.6g of sodium bisulfite, stirring and reacting at room temperature for 2.5h, then dropwise adding 80mL of an aqueous solution dissolved with 21.7g of potassium cyanide into the reaction solution under the cooling of an ice bath, removing the ice bath, stirring and reacting at room temperature for 2h, and purifying to obtain 4-methoxymandelonitrile; adding 24.5mL of 35% sulfuric acid, 4.56g of 4-methoxy mandelonitrile and 6.33g of phenol into another flask, heating to 50 ℃, stirring for reacting for 24 hours, and purifying to obtain 2- (4-hydroxyphenyl) -2- (4-methoxyphenyl) acetonitrile; adding 7.8g of 2- (4-hydroxyphenyl) -2- (4-methoxyphenyl) acetonitrile, 9.0g of potassium carbonate and 80mL of DMF into another flask, heating to 100 ℃ for reacting for 1h, adding 5.3mL of 3-chloro-1, 2-propanol, heating to 100 ℃, stirring and reacting for 1.5h to obtain an intermediate product; in another flask, 80mL of 5M aqueous sodium hydroxide solution and 8.3g of potassium ferricyanide were added, and 180mL of a methanol solution containing 7.51g of the intermediate product was slowly added dropwise, followed by stirring and reacting for 5min to purify the dicyanobenzenyl compound (a). 2-formylphenylboronic acid and polyether amine with the molecular weight of about 1000 are used as raw materials, the molar ratio of the raw materials to the polyether amine is controlled to be 2: 1, the raw materials are dissolved in a toluene solvent, a proper amount of sodium borohydride is added as a reducing agent, and the aminomethyl phenylboronic acid end-capped polyether amine is synthesized through a Petasis reaction. Trimethylolpropane and epoxypropane are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, hydroxyl-terminated three-arm polypropylene oxide is synthesized through cationic ring-opening polymerization, and then the hydroxyl-terminated three-arm polypropylene oxide and equimolar amount of acrylic acid are subjected to esterification reaction to obtain olefin-terminated three-arm polypropylene oxide.

Adding 0.04mol of dicyanobenzenyl compound (a) and 0.04mol of aminomethyl phenylboronic acid end-capped polyetheramine into a dry and clean reaction bottle, adding a proper amount of triethylamine, stirring and mixing uniformly, heating to 60 ℃ under the protection of nitrogen, reacting for 12h, then placing the mixture into a proper mold, placing the mold into a vacuum oven at 60 ℃ for 12h for further reaction and drying, cooling to room temperature, standing for 30min to obtain a polyether radical force response polymer, and crushing the polyether radical force response polymer into particles. 100g of polyether-based force-responsive polymer particles, 20g of hollow glass microspheres, 10g of divinylanthracene-type force-responsive filler (b), 10.0mg of BHT antioxidant, 15g of organobentonite and 6g of stearic acid are uniformly mixed, added into a small internal mixer for mixing for 15min, then added into an extruder for extrusion blending, the extrusion temperature is 120-130 ℃, and the obtained extruded sample strips are granulated to obtain the force-responsive foam particles.

Weighing 0.02mol of olefin-terminated three-arm polypropylene oxide, 0.02mol of 1, 3, 5-triacryloylhexahydro-1, 3, 5-triazine (c), 0.02mol of 1, 6-hexanedithiol, 0.02mol of trithiol compound (d) and 0.016mol of 4-bromobenzenesulfonic acid butyl ester (e), uniformly mixing, adding 0.2 wt% of benzoin dimethyl ether (DMPA) serving as a photoinitiator, stirring, fully mixing, and placing in an ultraviolet crosslinking instrument for ultraviolet radiation for 4 hours to obtain the dynamic polymer.

Weighing 50 parts by weight of force-responsive foam particles, 50 parts by weight of dynamic polymer samples, 10 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, performing hot-press molding by using hot air, setting the mold temperature at 110 ℃, the mold closing pressure at 10MPa, performing mold pressing for 10min, then releasing the pressure, cooling and demolding to obtain the composite material, wherein the composite material can be slowly expanded under the action of external force stretching and generates color change and fluorescence effect, and after the external force is removed, the composite material can be slowly recovered to the original shape and has the shape memory function. After the surface of the composite material has cracks or is damaged, the composite material is placed in a vacuum oven at the temperature of 80 ℃ for 2 hours, and the cracks disappear, so that the composite material has a self-repairing characteristic. In the embodiment, the material can be used as a sealing material with force-induced responsiveness in the field of electronic and electric appliances.

Example 18

AIBN is used as an initiator, and styrene and 4-vinylpyridine are subjected to free radical copolymerization to prepare the styrene-pyridine copolymer. Taking a compound (a), a compound (b), divinylbenzene and styrene as raw materials, taking cumyl dithiobenzoate as a chain transfer agent, carrying out RAFT copolymerization at the temperature of 110 ℃ to obtain modified polystyrene containing borane and phosphane side groups, and crushing the modified polystyrene into particles.

Uniformly mixing 90 parts by weight of modified polystyrene particles, 10 parts by weight of expandable microspheres (Expancel microspheres from Acksotbel company), 0.5 part by weight of diethyl azodicarboxylate, 0.08 part by weight of zinc borate, 8 parts by weight of sorbitan monolaurate and 0.05 part by weight of antioxidant 1010, adding the mixture into a double-screw extruder, controlling the head pressure to be 2Mpa, the extrusion temperature to be 200 ℃, controlling the water temperature of an underwater granulator to be 70 ℃, and carrying out underwater granulation to obtain the polystyrene foam particles.

Adding 200ml of dichloromethane solvent into a dry and clean reaction bottle, removing water and oxygen by introducing argon gas for 1h, adding 5g of styrene-pyridine copolymer and 0.61g of phenyl selenium bromide (c), stirring and mixing for 1h, putting the product into a proper mold, drying in a vacuum oven at 80 ℃ for 24h, finally obtaining dynamic polystyrene solid, and cutting the dynamic polystyrene solid into particles with uniform size.

Weighing 30 parts by weight of polystyrene foam particles and 70 parts by weight of dynamic polystyrene particles, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of adhesive, closing the mold, setting the mold temperature at 120 ℃, the mold closing pressure at 10MPa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material product. The tensile strength and elongation at break of the sample were measured according to DIN EN ISO 1856 (wherein the test rate was 100mm/min), the tensile strength of the sample was 7.16MPa, the elongation at break was 187%, both of which were greatly improved compared to the tensile strength (0.15MPa) and elongation at break (100%) of the conventional polystyrene foam article, and the resilience of the sample was 41% measured according to DIN 53512. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), and the transmitted impact force is 14.12kN, which has a good energy absorption effect. In the embodiment, the prepared composite material product can be used as a device shell to protect and buffer articles, and when the surface of the composite material product is damaged, the surface of the composite material product can be repaired by simple heating.

Example 19

The method comprises the steps of taking potassium persulfate as an initiator, taking an acrylate compound (a) and methyl acrylate as raw materials, obtaining polyacrylate containing azobenzene side groups through emulsion polymerization, reacting β -cyclodextrin with toluene-2, 4, 6-triyl triisocyanate to obtain a β -cyclodextrin polymer, taking diethylene glycol diacrylate and 3-mercaptophenylboronic acid as raw materials, controlling the molar ratio of the two to be 1: 2, taking AIBN as an initiator and triethylamine as a catalyst, obtaining a phenylboronic acid compound through a mercapto-Michael addition reaction, taking 4-hydroxystyrene and formaldehyde as raw materials, refluxing the phenylethene and zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, taking methanol as a solvent, taking AIBN as an initiator and triethylamine as a catalyst, obtaining a polyol compound through a thiol-olefin click addition reaction with pentaerythritol tetramercaptoacetate, taking polyethylene glycol 400 and acrylic acid as raw materials, obtaining double-bond-terminated polyethylene glycol through an esterification reaction, and then obtaining the double-bond-terminated polyethylene glycol through a thiol-olefin click addition reaction with 3-1, 2-propylene glycol.

100ml of 1, 4-dioxane solvent, 0.02mol of polyol compound (c) and 8mmol of 1, 2-diol-terminated polyethylene glycol are added into a three-neck flask, heated to 50 ℃, stirred and dissolved, then a proper amount of pyridine and 0.05mol of phenylboronic acid compound (b) are sequentially added, heated to 60 ℃ and reacted for 2 hours, so that a dynamic polymer is prepared, and the dynamic polymer is cut into particles with proper size. Weighing 100 parts by weight of dynamic polymer particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the dynamic polymer particles, the water and the magnesium pyrophosphate into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, heating the high-pressure reaction kettle to 118 ℃, keeping the pressure in the high-pressure reaction kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, finally opening a discharge valve at the bottom end of the high-pressure reaction kettle, taking out the foam particles, washing and air-drying.

Adding 8mmol of polyacrylate containing azobenzene side group and 100ml of 1, 4-dioxane solvent into a three-neck flask, heating to 50 ℃, stirring and dissolving, then adding 0.02mol of β -cyclodextrin polymer, adding a proper amount of triethylamine, heating to 100 ℃, reacting for 3 hours, and obtaining the dynamic polymer.

Weighing 40 parts by weight of dynamic polymer foam particles, 60 parts by weight of dynamic polymer samples, 2 parts by weight of talcum powder, 10 parts by weight of metal osmium heteroaromatic ring particles, 10 parts by weight of nano silver particles, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, then filling the premix into a proper mould, closing the mould, hot-pressing and forming by hot air, setting the temperature of the mould at 90 ℃, the mould closing pressure at 10Mpa and the mould pressing time at 10min, then releasing the pressure, cooling and demoulding to obtain the composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental speed is 100mm/min), the tensile strength of the sample is 3.18MPa, the elongation at break is 105%, the samples were tested for their resilience according to DIN53512 and had a resilience of 39%. The composite material has good processing formability and self-repairability, can generate heat under the action of infrared rays, can be used for manufacturing heat-conducting buffer gaskets by using obtained composite material samples, and is applied to the fields of automobile industry and various mechanical devices.

Example 20

An equimolar amount of amino cup [ 4]]Aromatic hydrocarbon reacts with toluene-2, 4, 6-triyl triisocyanate to prepare the calixarene modified diisocyanate. Using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and sequentially carrying out amidation and esterification on polyamide with the molecular weight of about 2,000 and 5-alkynyl caproic acid and propargyl alcohol with the same molar weight to obtain alkynyl terminated polyamide (a). Reacting 2 molar equivalents of 1-azido-6-phenylhexane with 1 molar equivalent of the alkynyl-terminated polyamide (a), adding N, N-isopropylamine, Cu (PPh)₃)₃Br was reacted as a catalyst at 60 ℃ for 12 hours with stirring to obtain phenylhexane terminated polyamide.

Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, carrying out bubbling deoxygenation for 1h by using argon, then adding 0.01mol of polyvinyl alcohol, 4mmol of 1, 4-phenyl diboronic acid and a proper amount of triethylamine into the reaction bottle, heating to 60 ℃ under a stirring state, reacting for 4h to prepare a dynamic polymer, and crushing the dynamic polymer into particles. Weighing 100 parts by weight of dynamic polymer particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the dynamic polymer particles, the water and the magnesium pyrophosphate into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, heating the high-pressure reaction kettle to 110 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, finally opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying.

Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, carrying out bubbling deoxygenation for 1h by using argon, then adding 0.1mol of calixarene modified diisocyanate and 0.1mol of polytrimethylene ether glycol into the reaction bottle, continuing to react for 2h, and then adding 0.1mol of phenylhexane terminated polyamide. After the reaction is finished, the solvent is removed by decompression and suction filtration, and then the dynamic polymer colloid is obtained by purification.

Weighing 60 parts by weight of dynamic polymer foam particles, 40 parts by weight of dynamic polymer colloid, 10 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA, 2 parts by weight of sodium dodecyl benzene sulfonate and 1 part by weight of stearic acid, adding the materials into a small internal mixer, mixing for 10min, filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material. The tensile strength and elongation at break of the samples were measured according to DIN EN ISO 1856 (where the test rate was 100mm/min), the tensile strength of the samples was 0.72MPa and the elongation at break was 398%, and the resilience of the samples was measured according to DIN53512 and was 32%. In the embodiment, the prepared composite material can be used for preparing a shock absorption and buffering foam protective gasket of an electronic appliance, can provide enough flexibility in the shock absorption process, and can repair a damaged part by heating.

Example 21

Trimethylolpropane and ethylene oxide are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, and hydroxyl-terminated three-arm polyethylene oxide is synthesized through cationic ring-opening polymerization.

Weighing 20g of hydroxyl-terminated polyethylene oxide in a dry and clean flask, heating to 110 ℃ for dewatering for 1h, adding 0.2g of polyurethane catalyst A-1, uniformly mixing, weighing 6.0g of TDI, quickly mixing, stirring and reacting, pouring into a proper mold, keeping the mold temperature at 56 ℃, opening the mold after 7min to obtain a polyurethane sample, cutting the polyurethane sample into polyurethane particles with proper size, adding the polyurethane particles into an extruder for extrusion and wire drawing, keeping the extrusion temperature at 150 ℃ and 170 ℃, printing the obtained silk sample by using a 3D printer, controlling the equipment melting temperature at 150 ℃, keeping the temperature for 15min, spraying out the silk sample by using a printer nozzle to print the silk sample into foam particles with a pneumatic dilatant structure and an outer skin structure, after printing, placing the silk sample in a constant-temperature oven for standing for a period of time, taking out and naturally cooling to obtain the polyurethane foam particles.

Weighing 4mmol of hydroxyl-terminated three-arm polyethylene oxide, dissolving in 200ml of tetrahydrofuran solvent, adding 0.04mol of terephthalaldehyde and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, performing reflux reaction at 65 ℃ for 6h under the protection of nitrogen, adding 0.02mol of polyether polyol ED-28, 4mmol of 2, 3-epoxypropyltrimethylammonium chloride, 3mmol of ethylene oxide potassium carboxylate and a small amount of boron trifluoride diethyl etherate, heating to 100 ℃, reacting for 4h, pouring a polymer solution with a certain viscosity into a mold, placing in a 60 ℃ oven for further reaction, cooling to room temperature, and standing for 30min to finally obtain the polyethylene oxide dynamic polymer colloid.

Weighing 50 parts by weight of polyurethane foam particles, 50 parts by weight of polyethylene oxide dynamic polymer colloid, 5 parts by weight of calcium carbonate and 2 parts by weight of titanium dioxide, premixing by using a stirrer, filling the premix into a proper mould, adding a proper amount of polyurethane adhesive, closing the mould, setting the temperature of the mould to be 90 ℃, the mould closing pressure to be 5Mpa and the mould pressing time to be 10min, then releasing the pressure, cooling and demoulding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.53MPa and the elongation at break is 273%, compared with the traditional polyurethane foam with similar tensile strength, the elongation at break is remarkably improved (20% → 273%), excellent toughness is expressed, and the resilience of the sample is detected according to DIN53512 standard, the rebound resilience is 48 percent, and the elastic resilience is good. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as 10.52s by a stopwatch. The prepared composite material has good rebound resilience and dilatancy, and can show different self-repairing performances and buffering characteristics under different temperatures and acid-base conditions.

Example 22

Taking potassium persulfate as an initiator, and carrying out free radical polymerization on 3-acrylamide dopamine and N-isopropyl acrylamide to obtain the dopamine-acrylamide copolymer. AIBN is used as an initiator, hydroxyethyl acrylate, 2-aminoethyl acrylate and acrylamide are used as raw materials, and the acrylamide-hydroxyl-amino copolymer is obtained through free radical polymerization.

Adding 3.0g of trimethyl borate into a dry and clean beaker, adding 120ml of deionized water, continuously stirring and dissolving at 50 ℃, adding a proper amount of triethylamine after complete dissolution, adjusting the pH value of the solution to 7.5-8, mixing for 10min, adding 6.0g of dopamine-acrylamide copolymer, continuously stirring to dissolve and mix in the process, heating to 50 ℃ for reaction for 3h after complete dissolution, removing the solvent by reduced pressure drying after the reaction is finished to obtain a polyacrylamide sample, and crushing the polyacrylamide sample into particles. Weighing 100 parts by weight of polyacrylamide sample particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the polyacrylamide sample particles, adding 40 parts by weight of supercritical carbon dioxide into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 105 ℃, keeping the pressure in the high-pressure reaction kettle at 20bar, maintaining the high-pressure reaction kettle at the temperature and the pressure for 2 hours, opening a discharge valve at the bottom end of the high-pressure reaction kettle, taking out foam particles, washing and air-drying.

Taking a dry and clean three-neck flask, adding 200ml of deionized water, then adding 24g of acrylamide-hydroxy-amino copolymer, 2.4g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, carrying out reflux reaction at 65 ℃ under the protection of nitrogen, then placing at 50 ℃ for 10 hours, and removing the solvent through reduced pressure drying to obtain a polyacrylamide sample.

Weighing 40 parts by weight of polyacrylamide foam particles, 60 parts by weight of a polyacrylamide sample, 2 parts by weight of bentonite, 2 parts by weight of an anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mould, closing the mould, setting the mould temperature at 80 ℃, the mould closing pressure at 5MPa, the mould pressing time at 10min, then releasing the pressure, cooling and demoulding to obtain a composite material product, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 0.80MPa, the elongation at break is 345%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 42%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as 8.13s by means of a stopwatch. The composite material can show dilatancy and buffer and absorb external impact force. In addition, the dynamic property and the buffering effect of the composite material can be adjusted by utilizing the pH buffer solution, so that the composite material is ensured to have the orthogonality regulation and control effect under different environmental conditions.

Example 23

1 molar equivalent of boron trifluoride diethyl etherate is used as an initiator, epichlorohydrin is used as an accelerator, ring-opening copolymerization of tetrahydrofuran and 2- (tetrahydrofuran-3-yl) acetonitrile is initiated, and water is used as a terminator to obtain hydroxyl terminated polytetrahydrofuran containing side nitrile groups.

Adding 10 parts by mass of polyether polyol ED-28, 2 parts by mass of 2, 3-epoxypropyltrimethylammonium chloride, 1.6 parts by mass of ethylene oxide potassium carboxylate, 0.05 part by mass of boron trifluoride diethyl etherate and 2.8 parts by mass of hexamethylene diisocyanate trimer into a reaction flask, heating to 100 ℃, reacting for 4 hours to obtain modified polyurethane, and cutting the modified polyurethane into particles with proper size. Weighing 100 parts by weight of modified polyurethane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the materials into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, heating the high-pressure reaction kettle to 118 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the temperature and the pressure for 2 hours, finally opening a discharge valve at the bottom end of the high-pressure kettle, taking out the foam particles, washing and air-drying.

Weighing 20g of hydroxyl-terminated polytetrahydrofuran containing side nitrile groups in a dry and clean flask, heating to 110 ℃ to remove water for 1h, then adding 3.5g of N, N-bis (2-hydroxyethyl) -9-anthracene benzylamine (a), 7.5g of diphenylmethane diisocyanate, 8g of acetone and 0.4g of stannous octoate, reacting for 3h under the protection of nitrogen at 80 ℃, removing the acetone in vacuum after the reaction is finished, cooling to room temperature to obtain a soft and elastic polyurethane sample, and curing and reacting for 2h under the condition of 350nm ultraviolet illumination to obtain the final dynamic polyurethane sample.

Weighing 40 parts by weight of polyurethane foam particles, 60 parts by weight of dynamic polyurethane sample, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, and adding the materials into a small internal mixer for mixing for 10 min; then weighing 100 parts by weight of the mixed materials, 400 parts by weight of water and 7 parts by weight of tricalcium phosphate, adding the mixed materials into an autoclave, injecting 25 parts by weight of supercritical carbon dioxide under the stirring state, heating the autoclave to 116 ℃, keeping the pressure in the autoclave at 20bar, maintaining the autoclave at the temperature and the pressure for 2 hours, finally opening a discharge valve at the bottom end of the autoclave to obtain a primary composite material, performing hot pressing to prepare the required composite foam material, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.55MPa, the elongation at break is 284%, compared with the traditional polyurethane foam with similar tensile strength, the elongation at break is remarkably improved (20% → 284%), and the excellent toughness is shown, the sample was tested for resilience according to DIN53512, which gave a resilience of 52% and a high resilience. The prepared composite foam material not only can show good plasticity, but also has good compression resilience, can be applied to sole materials or industrial machinery buffer sheets as a foam buffer cushion, and can show more excellent buffer performance when used under a heating condition, and can realize self-repairing by heating or illumination when cracks appear on the surface of the composite foam material.

Example 24

10g of 9-anthracenemethanol was dissolved in 100ml of pyridine solvent, cooled in an ice bath under an inert atmosphere, and then 50ml of undecylenoyl chloride was added thereto, and the mixture was stirred overnight at room temperature to obtain an anthracene derivative (a).

6.6g of p-phenylboronic acid and 50g of polydimethylsiloxane (with the molecular weight of 1000 and the viscosity of 600mPa & s at 25 ℃) are added into a dry and clean reaction bottle, a small amount of BHT antioxidant is dropwise added, the mixture is heated to 120 ℃ and mixed for 30min, a small amount of triethylamine is dropwise added, the reaction is carried out for 4h under the protection of nitrogen to prepare cross-linked polysiloxane, and the cross-linked polysiloxane is crushed into particles. Weighing 100 parts by weight of crosslinked polysiloxane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the crosslinked polysiloxane particles, adding 40 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 120 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying. An appropriate amount of PEG200 was measured, and 45 wt% of nano calcium carbonate (aspect ratio of 4, length of about 1 μm) was added thereto to obtain a dilatant dispersion. And pressurizing and soaking the prepared polysiloxane foam particles in the dilatant dispersion liquid for 2 hours, taking out the polysiloxane foam particles, wiping off residual liquid on the surface, and sintering the surface at a certain temperature to finally obtain the polysiloxane foam particles with dilatant properties.

100ml of methylmercaptosiloxane (b) with the molecular weight of about 30,000 is put into a dry and clean three-neck flask, after the temperature is raised to 80 ℃ and the mixture is stirred uniformly, 0.01 wt% of BHT antioxidant, 8g of anthracene derivative (a), 2.4g of 4-methyl-4-pentenoic acid, 1.0g of zinc trifluoromethanesulfonate and 0.2 wt% of photoinitiator DMPA are added and mixed for 1h, then the polymer is poured into a proper mould and is irradiated by 365nm ultraviolet light for 2h under nitrogen atmosphere, and then the mixture is placed for 30min under the condition of room temperature, and finally a dynamic polymer sample with certain viscoelasticity is obtained.

Weighing 50 parts by weight of polysiloxane foam particles with dilatancy, 50 parts by weight of dynamic polymer sample, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature at 110 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material, detecting the tensile strength and the elongation at break of the sample according to the DIN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 1.85MPa, the elongation at break is 347%, and detecting the resilience of the sample according to the DIN 53standard, wherein the resilience is 41%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured, and its recovery time was recorded as 11.82s using a stopwatch. The composite material shows viscosity under the action of low-speed impact force, and generates dilatancy under the action of high-speed impact force, so that impact energy is dispersed and absorbed; and (3) placing the damaged composite material sample in a vacuum oven at 80 ℃ for heating for 2-4h, or placing the sample in a certain frequency of illumination condition, wherein the sample can be bonded again, and the self-repairing property is embodied. In this embodiment, the prepared composite material can be used as an energy-absorbing protective material with self-repairing property.

Example 25

Using tert-butyl hypochlorite as an oxidant, oxidizing the urea azole of the urea azole compound (b) into triazolinedione, and reacting the triazolinedione-indole with indole-5-methanol to obtain a triazolinedione-indole compound (c). The polyoxypropylene triol is capped with toluene diisocyanate to produce the isocyanate-terminated polyether. Reacting 1 molar equivalent of triphenylmethane triisocyanate with equimolar amount of heptafluoro-2-naphthol to prepare isocyanate containing naphthol; 1 molar equivalent of triphenylmethane triisocyanate was reacted with an equimolar amount of benzyl alcohol to prepare benzyl alcohol-containing isocyanate.

Adding 8g of hexamethylene diisocyanate into a three-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, cooling to 45 ℃, adding 12mL of DMF for dissolving and diluting, introducing argon for protection, then dissolving 3.5g of a compound (a) and a small amount of butyl tin dilaurate ethyl ester solution into 40mL of DMF, dropwise adding the DMF into a reaction bottle at a constant speed, heating to 70 ℃ for reaction for 3h, adding 5g of polyoxypropylene triol (with the molecular weight of about 2,000Da), continuing to react for 6h at 70 ℃, then pouring reactants into a proper mold, placing the mixture into a vacuum oven at 80 ℃ for continuous reaction for 12h, cooling to room temperature, placing for 30min, preparing force-responsive polyurethane, and cutting the force-responsive polyurethane into particles with uniform size. Adding 100 parts by weight of force-responsive polyurethane particles, 400 parts by weight of water and 7 parts by weight of tricalcium phosphate into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, heating the high-pressure reaction kettle to 116 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the temperature and the pressure for 2 hours, opening a discharge valve at the bottom end of the high-pressure kettle, taking out the foam particles, washing and air-drying.

200ml of dichloromethane solvent is measured in a dry and clean reaction bottle, 20g of polytetrahydrofuran diol, 2.4g of triazolinedione-indole compound (c), 2.0g of isocyanate containing naphthol, 1.2g of isocyanate containing benzyl alcohol and 12g of isocyanate-terminated polyether are added, the mixture is stirred and mixed for 10min, heated to 60 ℃ for reaction for 30min, then the reaction solution is poured into a proper mold, placed in a vacuum oven at 80 ℃ for reaction and drying for 24h, cooled to room temperature, finally a dynamic polyurethane sample with good viscoelasticity is obtained, and the dynamic polyurethane sample is cut into particles with uniform size.

Weighing 30 parts by weight of force-responsive polyurethane foam particles, 70 parts by weight of dynamic polyurethane particles, 10 parts by weight of gallium-indium liquid alloy, 0.2 part by weight of talcum powder and 0.1 part by weight of dibutyltin dilaurate, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of polyurethane adhesive, closing the mold, setting the mold temperature at 90 ℃, the mold closing pressure at 10Mpa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to a DINEN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.78MPa, the elongation at break is 298%, compared with the traditional polyurethane foam with similar tensile strength, the tensile strength is remarkably improved in the aspect of the elongation at break (20% → 298%), excellent toughness is expressed, the rebound resilience of the sample is tested according to DIN53512, and the rebound resilience is 62 percent, and the sample has excellent high rebound resilience. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), and the transmitted impact force is measured to be 12.58kN, so that the composite material has a good energy absorption effect. The prepared composite material can be used as a functional heat-conducting buffer gasket for the shock absorption of precision instruments or electronic products, and can generate force-induced discoloration when being impacted by external force, thereby playing a warning role.

Example 26

Weighing 3g of terephthalaldehyde, dissolving in 50ml of absolute ethanol, adding 8.9g of diethyl malonate, 0.2g of piperidine and 0.2g of acetic acid, carrying out reflux reaction for 12 hours under the argon atmosphere, and then cooling and purifying to obtain the compound (a).

100g of ethylene propylene diene monomer particles (Dow's IP4770R), 20g of expandable microspheres (Expancel microspheres from Acksonobel), 1g of dicumyl peroxide, 10.0mg of BHT antioxidant, 15g of calcium carbonate, 10g of dioctyl phthalate, 6g of stearic acid, 5g of age inhibitor 4010NA, 6g of graphene and 2.5g of nano Fe₃O₄After being uniformly mixed, the mixture is added into a small internal mixer for mixing for 15min, and then the mixture is added into an extruder for extrusion blending, wherein the extrusion temperature is 120-The extruded sample strips were pelletized to prepare rubber-based foam pellets, which were then prepared into foam pellet sheets by hot press molding.

Adding a certain amount of chloroform solvent into a dry and clean reaction bottle, adding 5mmol of ethylene-vinyl alcohol copolymer and 0.01mol of boric acid, uniformly mixing, dropwise adding a small amount of triethylamine, heating to 110 ℃ for reaction for 2h, then adding 0.02mol of compound (a) and 0.03mol of triethylenetetramine into the reaction bottle, uniformly stirring, cooling to room temperature, standing for 6h, heating to 50 ℃ and standing for 10h, then pouring the mixture into a proper mold, performing compression molding by using a molding press at 100 ℃, cooling to room temperature, standing for 30min, and finally obtaining the dynamic polymer sheet.

Weighing a proper amount of foam particle sheets and dynamic polymer sheets, and bonding the foam particle sheets and the dynamic polymer sheets in a layer-by-layer alternating mode through an adhesive to obtain the composite material with the multilayer composite structure. The tensile strength and elongation at break of the samples were measured according to DIN EN ISO 1856 (where the test rate was 100mm/min), the tensile strength of the samples was 2.65MPa and the elongation at break was 283%, and the resilience of the samples was 46% according to DIN 53512. The obtained composite material has certain strength and toughness, can be expanded within a certain range, has certain tear resistance, can be slowly restored after external force is removed, has a shape memory function, and can be used as a heat sensing gasket.

Example 27

Dissolving 2g of selenocysteine hydrochloride into 120mL of dichloromethane, adding 5g of triethylamine under the stirring state, cooling to 0-5 ℃, slowly adding 2.5g of acryloyl chloride, stirring and reacting at room temperature for 24h under the protection of nitrogen, and carrying out reduced pressure distillation to obtain the N, N' -bis (acryloyl) selenocysteine. Using AIBN as an initiator, and carrying out free radical polymerization on N-isopropylacrylamide and 2-acrylic acid-3- (diethoxymethylsilyl) propyl ester to obtain the silane-acrylamide copolymer.

Weighing a certain amount of N-isopropyl acrylamide, dissolving the N-isopropyl acrylamide in deionized water to prepare 1mol/L solution, adding 1 mol% of a cross-linking agent indene dione derivative (a) and 0.6 mol% of an initiator potassium persulfate into the solution, stirring and mixing uniformly, standing for 1h to remove bubbles, placing the mixture in a constant-temperature water bath at the temperature of 60 ℃ for reaction for 7h to prepare the force-responsive polyacrylamide, and crushing the force-responsive polyacrylamide into particles. Weighing 100 parts by weight of force-responsive polyacrylamide sample particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the materials into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, heating the high-pressure reaction kettle to 105 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the temperature and the pressure for 2 hours, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying.

Weighing 100ml of deionized water in a dry and clean beaker, adding 7.1g N-isopropyl acrylamide, 0.26g of N, N' -bis (acryloyl) selenocysteine and 0.27g of initiator potassium persulfate, stirring and mixing uniformly, standing for 1h to remove bubbles, and placing in a constant-temperature water bath at 60 ℃ for reaction for 5h to prepare a first network polymer; and then adding 0.6g of ammonium metaborate, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, mixing for 10min, adding 3g of silane-acrylamide copolymer, continuously stirring to dissolve and mix in the process, heating to 50 ℃ to react for 3h after complete dissolution, stirring for 30min at 60 ℃, adding 0.2g of bentonite, and continuously stirring and mixing at 60 ℃ to react for 3 h. And pouring the viscous polymer solution into a proper mould, placing the mould in a vacuum oven at 50 ℃ for continuous reaction for 4h, then cooling to room temperature and placing for 30min to finally obtain the dynamic polymer colloid.

Weighing 40 parts by weight of polyacrylamide foam particles and 60 parts by weight of dynamic polymer colloid, premixing by using a stirrer, filling the premix into a proper mold, closing the mold, setting the mold temperature at 80 ℃, the mold closing pressure at 5Mpa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material product, and detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 0.80MPa, the elongation at break is 478 percent, and the composite material product has excellent tensile toughness. The composite material has good flexibility and deformability and has the capability of mechanochromism, and the obtained composite material can be used as a stress indicating material and applied to the field of electronics and electricity.

Example 28

4-aminophenylboronic acid and dopamine in equal molar amounts are taken as raw materials, tetrahydrofuran is taken as a solvent, and an amino-terminated compound (a) is obtained through condensation reaction at the temperature of 60 ℃.

30g of polyetheramine 2,000 and 2.5g of amino-terminated compound (a) are weighed in a dry and clean flask, heated to 100 ℃, introduced with nitrogen to remove water and remove oxygen for 1h, then 17g of tetrathiafulvalene-containing isocyanate compound is added, and the mixture reacts for 2h under the condition of 80 ℃ nitrogen protection to prepare modified polyurea which is cut into particles with uniform size. Then weighing 100 parts by weight of polyurea particles, 400 parts by weight of water and 7 parts by weight of tricalcium phosphate, adding the polyurea particles, the water and the tricalcium phosphate into a high-pressure reaction kettle, injecting 40 parts by weight of supercritical carbon dioxide in a stirring state, then heating the high-pressure reaction kettle to 116 ℃, keeping the pressure in the high-pressure kettle at 20bar, then maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, finally opening a discharge valve at the bottom end of the high-pressure kettle, taking out the foam particles, washing and air-drying.

A dry and clean reaction flask was charged with 3mmol of polyoxypropylene triol having a molecular weight of about 5,000, 1.5mmol of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) ethylenediamine (b) and 6mmol of 1, 2-bis (4-phenylisocyanate) disulfide, and the reaction was continued for 2 hours to obtain a polyurethane-based dynamic polymer elastomer, which was cut into uniform-sized particles.

Weighing 30 parts by weight of polyurea foam particles and 70 parts by weight of polyurethane-based dynamic polymer elastomer particles, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of polyurethane adhesive, closing the mold, setting the temperature of the mold to be 90 ℃, the mold closing pressure to be 5Mpa, and the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 2.21MPa, the elongation at break is 208%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 52%. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), and the transmitted impact force is measured to be 13.18kN, so that the composite material has a good energy absorption effect. By virtue of good rebound resilience and buffering capacity of the composite material, the composite material can be used as an energy-absorbing buffer gasket for damping and silencing of precision instruments or electronic products.

Example 29

Adding 2mol of 1, 1, 1, 3, 3, 3-hexamethyldisilazane and 2mol of 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine into a nitromethane solution, heating to 50 ℃, stirring for reaction, adding 2mol of sodium acetate and DMF under a nitrogen atmosphere to prepare an intermediate product, cooling the reaction solution to 0 ℃, dropwise adding 1mol of disulfide dichloride, continuously stirring for reaction for 15min, pouring into cold water, collecting the product, dissolving in n-hexane, and adding Na₂SO₄Drying, purifying, dissolving the product in methanol solvent, adding appropriate amount of K₂CO₃The mixture was stirred at room temperature for 4 hours, purified and recrystallized from methanol to obtain the dihydroxy compound (a). Taking methylene dithio-dimethanol and ethylene oxide as raw materials, and KOH as a catalyst, and synthesizing hydroxyl-terminated polyethylene oxide through cationic ring-opening polymerization.

Weighing 30g of polyurethane foam particles, 20g of hydroxyl-terminated polyethylene oxide, 4.8g of dihydroxy compound (a) and 8.4g of TDI-TMP adduct, uniformly mixing by using a stirrer, filling the mixture into a proper mould, closing the mould, setting the temperature of the mould to be 60 ℃, the closing pressure to be 2Mpa and the mould pressing time to be 60min, then releasing the pressure, cooling and demoulding to obtain a composite material product, and detecting the rebound rate of a sample according to DIN53512 standard, wherein the rebound rate is 49%. The prepared composite material has certain compression resilience, can be applied to automobile parts as a damping and shock-absorbing material, plays roles in reducing noise and vibration, and can realize self-repairing by heating when cracks appear on the surface of the composite material.

Example 30

Taking potassium persulfate as an initiator and 4-hydroxybutyl acrylate and methyl acrylate as raw materials, and obtaining the copolymerization modified acrylate (a) through free radical polymerization.

Adding a certain amount of toluene solvent into a dry and clean three-neck flask, adding 0.03mol of copolymerization modified acrylate (a) and 0.75 mol% of siloxane compound (b), stirring and mixing for 10min, and reacting for 12h under the condition of 80 ℃ nitrogen protection to obtain an acrylate polymer 1; adding 100 parts by weight of acrylate polymer 1, 1 part by weight of barite powder, 2 parts by weight of gypsum and 0.05 part by weight of antioxidant 168 into a screw extruder, uniformly mixing, extruding and granulating to obtain acrylate particles suitable for foaming, finally adding the particles into a charging barrel of a first extruder, heating and melting at 160 ℃, injecting supercritical carbon dioxide into the tail end of the first extruder, wherein the injection weight ratio of materials to the supercritical carbon dioxide per hour is controlled to be 100: 20, injecting the mixed polymer/high-pressure fluid melt into a second extruder through a melt pump, gradually cooling, uniformly mixing, extruding and foaming from a port die of the second extruder, and preparing the acrylate foam particles through underwater granulation.

Weighing 3 molar equivalents of the compound (c) and 2 molar equivalents of tris (2-aminoethyl) amine in a ball mill, uniformly mixing, grinding for 45min, cooling to room temperature, and standing for 6h to obtain a dynamic polymer sample.

Weighing 40 parts by weight of acrylic ester foam particles, 60 parts by weight of a dynamic polymer sample, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer, mixing for 5min, filling the premix into a proper mold, closing the mold, performing hot press molding by using hot air, setting the temperature of the mold to be 110 ℃, the closing pressure to be 10MPa, the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain the composite heat conduction material, pressing the product (80 x 20mm) to 75% of the thickness by hand, keeping the product for 60s, then slowly releasing the product, measuring the time required by the sample to recover to a deformation position with the initial thickness of 5%, and recording the recovery time to be 7.64s by using a stopwatch. When knocking the sample fast, it can demonstrate interim rigidity, plays the effect of dissipation stress, when appearing damaged on its surface, can carry out the selfreparing to damaged department through the heating again, can be applied to body-building apparatus with it as the protection pad that shocks resistance that can selfrepare.

Example 31

Adding a proper amount of 2-mercaptoethanol and petroleum ether into a reaction bottle, cooling to 0 ℃ by using an ice-water bath, dropwise adding a mixed solution of disulfide dichloride and petroleum ether, controlling the molar ratio of 2-mercaptoethanol to disulfide dichloride to be 3: 1, continuously stirring for 4 hours after the addition is finished, washing the reaction mixture by using distilled water, separating out an organic phase, drying by using anhydrous calcium chloride, decompressing and distilling the petroleum ether by using a water pump at room temperature, and decompressing and distilling under the heating of the water bath to obtain the bis (2-hydroxy) ethyl tetrasulfide (a). Adding a certain amount of selenium into an aqueous solution dissolved with sodium borohydride under a stirring state, stirring and reacting for 25min, and then keeping the temperature through a short steam bath to ensure that the selenium is completely dissolved to obtain a brownish red sodium diselenide solution; then adding the sodium diselenide solution into an anhydrous tetrahydrofuran solution dissolved with 2-bromoethanol under the protection of nitrogen, and reacting for 6 hours at 50 ℃ to obtain a yellow transparent 2, 2' -diselenide diethylene glycol solution (b). The low molecular weight ethylene propylene rubber is used as a raw material, dibenzoyl peroxide is used as a cross-linking agent to react to form a small cluster structure, and maleic anhydride is grafted on the surface of the cluster to obtain the maleic anhydride grafted ethylene propylene rubber.

Uniformly mixing 100g of ethylene propylene diene monomer particles, 20g of hollow glass microspheres, 10.0mg of BHT antioxidant, 15g of organobentonite, 6g of stearic acid, 2g of zinc oxide, 1.0g of benzoyl peroxide and 1.5g of anti-aging agent 4010NA, adding the mixture into a small internal mixer for mixing for 15min, adding the mixture into an extruder for extrusion blending, wherein the extrusion temperature is 120-130 ℃, and granulating the obtained extruded sample strips to obtain the skin-carrying polymer foam particles.

Weighing 5.5g of maleic anhydride grafted ethylene propylene rubber, adding into a reaction bottle, adding 30ml of epoxidized soybean oil, 10ml of tricresyl phosphate, 2.52g of bis (2-hydroxy) ethyl tetrasulfide (a), 2.48g of 2, 2' -diselenyl diethanol (b), 0.04g of p-toluenesulfonic acid, 1.0mg of BHT antioxidant, 1.0g of montmorillonite and 1.2g of carbon black, introducing nitrogen for protection, heating to 80 ℃, stirring for reaction for 2 hours, then placing the reaction liquid into a proper mold, continuing the reaction for 5 hours in a vacuum oven at 80 ℃, cooling to room temperature, standing for 30 minutes, taking out a sample from the mold, and obtaining the ethylene propylene rubber dynamic polymer.

Weighing 20 parts by weight of skinned polymer foam particles, 80 parts by weight of ethylene propylene rubber dynamic polymer, 2 parts by weight of zinc oxide, 2 parts by weight of anti-aging agent 4010NA, 2 parts by weight of maleic anhydride grafted ethylene propylene rubber and 1 part by weight of stearic acid, adding the materials into a small internal mixer, mixing for 15min, filling the premix into a proper mold, closing the mold, hot air hot-pressing for molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the rebound rate of a sample according to DIN53512 standard, wherein the rebound rate is 52%, and the composite material can show good rebound resilience. The composite material is subjected to an impact test according to EN1621-2012 standard (the sample thickness is 10mm, the test height is 50cm), and the transmitted impact force is 14.34kN, which has a good energy absorption effect. In this embodiment, the composite material can be used as an energy-absorbing and shock-absorbing pad for manufacturing shoes or sports goods, and the material can show different buffering and shock-absorbing effects under illumination and heating conditions, and has orthogonality and cooperativity.

Example 32

Mixing and dissolving equal molar amount of cyclooctadiene and m-chloroperoxybenzoic acid in a certain amount of acetonitrile solvent, dropwise adding a proper amount of H₂SO₄Stirring and reacting at room temperature to obtain 5-cyclooctene-1, 2-diol; the polyoctene polyol and cyclooctene are mixed in a molar ratio of 1: 2, and under the action of a Grubbs second-generation catalyst (1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium), the polyoctene polyol is prepared. 2-formylphenylboronic acid and methylamine are used as raw materials, toluene is used as a solvent, sodium borohydride is used as a reducing agent, the (2- (methylamino) methyl) phenylboronic acid is synthesized through a Petasis reaction, and then the (2- (methylamino) methyl) phenylboronic acid is respectively subjected to alkylation reaction and esterification reaction with 1, 6-dibromohexane and 1, 2-diol propane to prepare the aminomethyl phenylboronic acid ester compound (a), wherein the alkylation reaction solvent is DMF, the catalyst is potassium carbonate, the reaction temperature is 90 ℃, the esterification reaction catalyst is anhydrous sulfuric acid, and the reaction temperature is 90 ℃. And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polyethylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polyethylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10.

Weighing 20g of graft modified low molecular weight polyethylene and 20mg of BHT antioxidant, adding the materials into a dry clean three-neck flask, heating to 160 ℃ under the protection of nitrogen, stirring and melting, then adding 2.0g of parallel composite force sensitive groups (b), 0.5g of 8-hydroxy benzo [ a ] pyrene, 0.15g of p-toluenesulfonic acid, 2.0g of plasticizer DOP and 0.25g of dimethyl silicone oil, and continuing to react for 3 hours under the condition of nitrogen. Then pouring the mixture into a proper mould, carrying out compression molding by using a molding press at 120 ℃, then cooling to room temperature and standing for 30min to finally obtain the force response polyethylene, and crushing the force response polyethylene into granules. 100g of force-responsive polyethylene particles, 20g of hollow glass microspheres, 10.0mg of BHT antioxidant, 6g of stearic acid, 5g of zinc oxide and 1.5g of anti-aging agent 4010NA are uniformly mixed, added into an extruder for extrusion blending, the extrusion temperature is 120-130 ℃, and the obtained extruded sample strips are granulated to obtain the skin-carrying polymer foam particles.

Dissolving 5.4g of polyoctenamei polyol in 100ml of toluene solvent, adding 4mg of BHT antioxidant, mixing and stirring uniformly, adding 1.0 mol% of aminomethyl phenylboronic acid ester compound (a), dropwise adding a small amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a certain amount of triethylamine, heating to 65 ℃, continuing stirring and reacting for 2h, pouring the polymer solution into a proper mould, drying in a vacuum oven at 50 ℃ for 12h to remove the solvent, cooling to room temperature, standing for 30min, and finally obtaining a colloidal dynamic polymer sample.

Weighing 40 parts by weight of skinned polymer foam particles, 60 parts by weight of a dynamic polymer sample, 2 parts by weight of zinc oxide, 2 parts by weight of an anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, then filling the premix into a proper mold, closing the mold, hot air hot press molding, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa, the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 5.98MPa, the elongation at break is 278%, detecting the resilience of the sample according to DIN53512 standard, the resilience is 58%, and the composite material can show good resilience, and can be quickly knocked, the material exhibits temporary rigidity. The composite was subjected to an impact test according to standard EN1621-2012 (sample thickness 10mm, test height 50cm) and the transmitted impact force was measured to be 16.58 kN. In the embodiment, the obtained polymer material can be used for manufacturing an efficient damping material, is applied to impact resistance protection, and can generate a force-induced toughening effect under the action of mechanical force.

Example 33

Taking vinyl boronic acid pinacol ester and cyclopentadiene as raw materials, controlling the molar ratio of the vinyl boronic acid pinacol ester to the cyclopentadiene to be 1: 1, and taking aluminum trichloride as a catalyst to prepare boric acid ester modified norbornene (b) through a Diels-Alder reaction; dipropylene glycol diacrylate and cyclopentadiene are used as raw materials, the molar ratio of the dipropylene glycol diacrylate to the cyclopentadiene is controlled to be 1: 2, and aluminum trichloride is used as a catalyst to prepare the norbornene compound (d) through a Diels-Alder reaction. 150ml of toluene solvent is added into a dry and clean reaction bottle, then 0.02mol of borate modified norbornene (b) and 4mmol of norbornene compound (d) are added, metallocene catalyst/methylaluminoxane is taken as a catalytic system, and the crosslinking polynorbornene compound with the borate lateral group is prepared by addition polymerization reaction at 70 ℃.

Adding 0.2mol of hydroxyl-terminated polybutadiene, 0.2mol of rhodamine derivative (a) and 0.2mol of 2, 2' -diselendiethanol (c) into a dry and clean reaction bottle, uniformly dissolving, adding 0.4mol of toluene-2, 4, 6-triyl triisocyanate, stirring at room temperature for 24 hours to react to prepare a force-responsive polymer, and crushing the force-responsive polymer into particles. Weighing 100g of force-responsive polymer particles, 20g of hollow glass microspheres, 10mg of BHT antioxidant, 15g of carbon black and 1.5g of antioxidant 4010NA, uniformly mixing, adding into a small internal mixer, mixing for 20min, adding into an extruder, extruding and blending at the extrusion temperature of 120-130 ℃, and granulating the obtained extruded sample strip to obtain the force-responsive foam particles.

Adding 200ml of o-dichlorobenzene solvent into a dry and clean reaction bottle, adding 0.02mol of ammonium borate, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, adding 5mmol of crosslinked polynorbornene compound with a boric acid ester side group, stirring and mixing for 10min, adding a small amount of anhydrous sodium sulfate, heating to 80 ℃, stirring and reacting for 3h, pouring the mixture into a proper mold, placing the mixture in a vacuum oven at 60 ℃ for continuing to react for 12h, cooling to room temperature, and standing for 30min to finally obtain a colloidal dynamic polymer sample.

Weighing 60 parts by weight of force-responsive foam particles, 40 parts by weight of a dynamic polymer sample, 5 parts by weight of carbon black, 2 parts by weight of an anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, then filling the premix into a proper mold, closing the mold, carrying out hot-press molding by using hot air, setting the mold temperature at 90 ℃, the mold closing pressure at 10MPa, carrying out mold pressing for 10min, then carrying out pressure relief, cooling and demolding to obtain a composite material sample, carrying out a tensile test by using a tensile testing machine, and irradiating the material by using ultraviolet light of 340nm in the tensile process to firstly emit green fluorescence; and (3) continuously stretching, when the elongation rate exceeds 50%, the green fluorescence is gradually weakened, the red fluorescence is gradually enhanced, and the fractured sample can be heated to realize self-repairing through wetting the fracture surface. The composite material can be used for stress warning materials, and reminds managers to maintain the materials, so that safety is guaranteed.

Example 34

Trimethylolpropane and propylene oxide are used as raw materials, KOH is used as a catalyst, hydroxyl-terminated polypropylene oxide is synthesized through cationic ring-opening polymerization, 1 molar amount of hydroxyl-terminated three-arm polypropylene oxide and 3 molar amounts of acrylic acid are subjected to esterification reaction to obtain three-arm polypropylene oxide triacrylate, and the three-arm polypropylene oxide triacrylate and 3 molar amounts of 3-mercapto-1, 2-propanediol are subjected to thiol-ene click reaction to obtain the 1, 2-diol-terminated three-arm polypropylene oxide.

Adding a certain amount of NMP solvent into a dry and clean reaction bottle, adding 0.03mol of hydrazide-terminated polyethylene glycol, heating to 60 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.02mol of 1, 3, 5-benzenetricarboxylic aldehyde, and reacting for 24h under the protection of nitrogen to form a first network; then 0.03mol of polyetheramine D2,000, 6mmol of paraformaldehyde is added, the mixture is heated to 50 ℃ under the stirring state for reaction for 30min, finally the polyether elastomer with the double-network structure is obtained, and the polyether elastomer is crushed into particles. Uniformly mixing 90 parts by weight of polyether elastomer particles, 10 parts by weight of foamable microspheres (Expancel microspheres from Acksonobel company), 0.08 part by weight of silicon dioxide, 8 parts by weight of sorbitan monolaurate and 0.05 part by weight of antioxidant 1010, adding the mixture into a double-screw extruder, controlling the pressure of the extruder head to be 2Mpa, the extrusion temperature to be 160 ℃, controlling the water temperature of an underwater granulator to be 70 ℃, and carrying out underwater granulation to obtain the polyether foam particles.

Adding 0.03mol of triethyl borate into a dry and clean reaction bottle, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, then adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 0.02mol of 1, 2-diol-terminated three-arm polypropylene oxide, uniformly mixing, reacting for 3h at 60 ℃, then pouring the reaction solution into an appropriate mold, placing in a vacuum oven at 60 ℃ for 24h for further reaction and drying, then cooling to room temperature, and standing for 30min to finally obtain a dynamic polymer sample.

Weighing 40 parts by weight of polyether foam particles, 60 parts by weight of dynamic polymer sample, 5 parts by weight of graphene, 1 part by weight of montmorillonite, 1 part by weight of silicon dioxide, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 15min, then filling the premix into a proper mold, closing the mold, carrying out hot air hot press molding, setting the mold temperature at 120 ℃, the mold closing pressure at 10MPa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain the composite material. The tensile strength and elongation at break of the samples were measured according to DIN EN ISO 1856 (where the test rate was 100mm/min), the tensile strength of the samples was 3.94MPa and the elongation at break was 183%. In the embodiment, the composite material can be prepared into a graphene conductive buffer material for use, and external acting force can be sensed and monitored by measuring the conductivity of the material under the action of stress; when cracks are generated on the surface of the sample, the sample can be self-repaired by heating.

Example 35

Adding a certain amount of anhydrous toluene into a reaction bottle, adding 5g of polyethylene glycol 800 and a proper amount of tert-butyl alcohol solution dissolved with potassium tert-butoxide, uniformly mixing, introducing nitrogen for 20min, dropwise adding 3ml of ethyl bromoacetate, stirring at room temperature for 24h, dissolving in a methanol solvent after purification, slowly adding a hydrazine hydrate methanol solution, stirring at room temperature for 24h, filtering and purifying to obtain the hydrazide-terminated polyethylene glycol.

70 parts by weight of thermoplastic polyurethane particles (1185A, Germany BASF), 20 parts by weight of hollow glass microspheres, 10 parts by weight of spirothiopyran crystals, 6 parts by weight of stearic acid, 0.3 part by weight of talcum powder and 0.05 part by weight of antioxidant 1010 are uniformly mixed, and then the mixture is added into a screw extruder to be granulated to obtain the force-responsive polyurethane particles.

Measuring 200ml of tetrahydrofuran solvent in a reaction bottle, adding 0.03mol of tri-tert-butyl borate, dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, then adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, shaking and mixing for 10min, then adding 0.04mol of polyoxypropylene triol with the molecular weight of about 2,000, shaking and mixing uniformly, and reacting for 3h at 50 ℃ to obtain a first network; and introducing nitrogen to remove water and oxygen for 1h, adding 0.03mol of hydrazide-terminated polyethylene glycol and 0.02mol of 1, 3, 5-benzenetricarboxylic aldehyde, heating to 60 ℃ under the protection of nitrogen, and reacting for 24h to obtain the dynamic polymer with the double networks.

Weighing 40 parts by weight of force-responsive polyurethane particles, 60 parts by weight of dynamic polymer sample, 2 parts by weight of talcum powder, 10 parts by weight of graphene, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding into a small internal mixer, mixing for 10min, then filling the premix into a proper mould, closing the mould, hot-pressing and forming by hot air, setting the temperature of the mould at 90 ℃, the mould closing pressure at 10Mpa and the mould pressing time at 10min, then releasing the pressure, cooling and demoulding to obtain the composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental speed is 100mm/min), the tensile strength of the sample is 2.55MPa, the elongation at break is 290%, the rebound resilience of the sample is 49 percent according to DIN53512, and the sample shows certain rebound resilience and good thermal stability. In this embodiment, the composite material may be made into a graphene conductive material for use, and the external acting force and the environment can be sensed and monitored by measuring the electrical conductivity of the material under the stress action in different environments.

Example 36

Taking a compound (a), a compound (b) and styrene as raw materials, taking dithiobenzoic acid cumyl ester as a chain transfer agent, and carrying out RAFT copolymerization at 110 ℃ to obtain the polystyrene containing borane and phosphane side groups.

Adding 90 parts by weight of polystyrene, 10 parts by weight of tetraarylethylene type force-responsive filler (c), 1.5 parts by weight of barium sulfate, 1 part by weight of talcum powder and 0.05 part by weight of antioxidant 168 into a screw extruder, uniformly mixing, and carrying out extrusion granulation to obtain the force-responsive polystyrene granules. Uniformly mixing 90 parts by weight of polystyrene particles, 10 parts by weight of foamable microspheres (Expancel microspheres from Acksonobel company), 0.08 part by weight of zinc borate, 8 parts by weight of sorbitan monolaurate and 0.05 part by weight of antioxidant 1010, adding the mixture into a double-screw extruder, controlling the pressure of the extruder head to be 2Mpa, the extrusion temperature to be 200 ℃, controlling the water temperature of an underwater granulator to be 70 ℃, and carrying out underwater granulation to obtain the polystyrene foam particles.

Adding 200ml of toluene solvent into a dry and clean reaction bottle, introducing argon to remove water and oxygen for 1h, adding 8g of styrene, 1g of 4-vinylphenylboronic acid, 0.65g of divinylbenzene, 0.1g of photoinitiator DMPA and 1.2 wt% of benzoyl peroxide, heating to 80 ℃ under the protection of argon to react for 5h, adding a small amount of anhydrous sodium sulfate, and continuing to heat to react for 2h to form a first network; then 5g of polystyrene containing borane and phosphine side groups and 1.74g of diethyl azodicarboxylate are added to continue to react for 1h, and then the product is placed in a proper mould to be dried in a vacuum oven at 80 ℃ for 24h to finally obtain a dynamic polystyrene sample which is cut into particles with uniform size.

Weighing 30 parts by weight of polystyrene foam particles and 70 parts by weight of dynamic polystyrene particles, premixing by using a stirrer, filling the premix into a proper mold, adding a proper amount of adhesive, closing the mold, setting the mold temperature at 120 ℃, the mold closing pressure at 10Mpa and the mold pressing time at 10min, then releasing the pressure, cooling and demolding to obtain a composite material product, detecting the tensile strength and the elongation at break of a sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 5.28MPa, the elongation at break is 87%, detecting the rebound of the sample according to DIN53512 standard, and the rebound is 47%. The sample can show a remarkable fluorescence change under ultraviolet light in a stretching or compressing process, and can be used for manufacturing electronic instrument devices with self-repairing and force-induced response characteristics.

Example 37

Adding 5g of benzophenone, 20g of maleic anhydride and 100ml of acetonitrile solvent into a reactor, mixing and stirring uniformly, introducing argon for protection, irradiating for 5 hours by using a 450W mercury-pressing arc lamp, distilling and purifying to obtain a bicyclo [4.2.0] octane compound (a), reacting with ethylene glycol, adding concentrated sulfuric acid as a catalyst, reacting for 12 hours under the condition of 100 ℃ argon protection, purifying and drying to obtain the bicyclo [4.2.0] octane compound (b). Adding 0.02mol of 2, 2, 4-trimethylhexane diisocyanate into a three-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, cooling to 45 ℃, adding 12mL of DMF for dissolving and diluting, introducing argon for protection, dissolving 0.01mol of N, N-bis (2-hydroxyethyl) cinnamamide and a small amount of butyl tin dilaurate ethyl ester solution in 40mL of DMF, dropwise adding the DMF into a reaction bottle at a constant speed, heating to 70 ℃ for reaction for 3h, adding 0.01mol of polyethylene glycol 400, and continuing the reaction for 6h at 70 ℃ to obtain the polyurethane containing cinnamamide side groups.

20g of polytetrahydrofuran glycol PTMG-1000, 3.2g of bicyclo [4.2.0] octane compound (b), 2.0g of dicyanocyclobutane compound (c) and 18g of toluene-2, 4, 6-triyl triisocyanate are added into a dry and clean reaction bottle, uniformly stirred, heated to 100 ℃ for reaction for 1h, then 2.2g of pentaerythritol tetramercaptoacetate is added, the mixture is fully stirred and mixed, then the reactant is placed into a proper mold, and placed into a vacuum oven at 60 ℃ for 12h for further reaction and drying, thus obtaining the polyurethane-based polymer, and the polyurethane-based polymer is crushed into particles. Adding 90 parts by weight of polyurethane-based polymer particles, 3 parts by weight of calcium carbonate, 1.5 parts by weight of silicon dioxide, 0.05 part by weight of antioxidant 168, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid into a small internal mixer, mixing for 15min, adding into a charging barrel of a first extruder, heating and melting at 160 ℃, injecting supercritical nitrogen into the tail end of the first extruder, wherein the injection weight ratio of the materials to the supercritical nitrogen per hour is controlled at 100: 30, injecting the mixed polymer/high-pressure fluid melt into a second extruder through a melt pump, gradually cooling, uniformly mixing, extruding and foaming from a port die of the second extruder, and preparing the polyurethane foam particles through underwater granulation.

Adding a certain amount of dichloromethane solvent into a reaction bottle, adding 5mmol of 1, 2-bis (chlorodimethylsilyl) ethane, 4mmol of polyethylene glycol 800 and 5mmol of sodium borate, dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, adding a proper amount of triethylamine, heating to 80 ℃, reacting for 4h, then adding 10g of polyurethane containing cinnamamide side groups, continuing to react for 1h, pouring the reaction solution into a proper mold, and irradiating for 30min under 280nm ultraviolet light to obtain a dynamic polymer sample.

Weighing 40 parts by weight of polyurethane foam particles, 60 parts by weight of a dynamic polymer sample, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mould, closing the mould, performing hot-press molding by using hot air, setting the mould temperature at 110 ℃, the mould closing pressure at 10Mpa and the mould pressing time at 10min, then releasing the pressure, cooling and demoulding to obtain a composite material, detecting the rebound rate of the sample according to the DIN53512 standard, wherein the rebound rate is 58 percent, the composite material has excellent high rebound resilience, the bicyclo [4.2.0] octane and cyclobutane structures in the composite material can form a linear alkane structure containing double bonds through ring opening under the action of external force, and the added mercaptan compound can be used as a crosslinking agent to enable the material to realize force induced crosslinking under the action of external force, and the existence of dynamic covalent bonds enables the composite material to have a certain self-repairing capability.

Example 38

Hydroxyl-terminated methyl vinyl siloxane with the molecular weight of about 3,000 and 3-mercapto-1-propanol are taken as raw materials, a proper amount of DMPA is added to be taken as a photoinitiator, and the modified siloxane (a) is prepared through a thiol-ene click reaction under the condition of ultraviolet irradiation. Using ethanethiol and isocyanate ethyl acrylate as raw materials, reacting to obtain acrylate containing thiocarbamate groups, and reacting the acrylate with methyl mercapto siloxane with molecular weight of about 30,000 by taking DMPA as a photoinitiator to prepare hydrogen bond group grafted modified siloxane (c) through thiol-ene click reaction under the condition of ultraviolet irradiation.

Into a three-necked flask were charged 40g of the modified siloxane (a), 1.7g of the siloxane compound (b), 1.96g of pimeloyl chloride and 2.0g of silica, heated to 80 ℃ to react for 8 hours, then cooled to room temperature and left to stand for 30 minutes to prepare a crosslinked polysiloxane, which was then crushed into pellets. Weighing 100 parts by weight of crosslinked polysiloxane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the crosslinked polysiloxane particles, adding 40 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 120 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying.

Weighing 70 parts by weight of polysiloxane foam particles, 30 parts by weight of a hydrogen bond group graft modified siloxane sample, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, uniformly mixing by using a stirrer, filling into a proper mould, closing the mould, setting the mould temperature at 60 ℃, the mould closing pressure at 2MPa, the mould pressing time at 60min, then releasing the pressure, cooling and demoulding to obtain a composite foam material product, and detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 1.98MPa, and the elongation at break is 375%. The surface of the composite material has certain viscosity, excellent tensile toughness can be shown through the synergistic effect of dynamic covalent bonds and hydrogen bonds in the foam material, the material is slightly heated after being pulled apart, a broken sample can be bonded again, and the composite foam material can be used as a recyclable shoe material filling material.

Example 39

Taking methyl mercapto siloxane with molecular weight of about 30,000 and dimethyl dithio-amino-formic allyl ester as raw materials, taking DMPA as a photoinitiator, and preparing the siloxane (a) containing disulfide ester side groups by thiol-ene click reaction under the condition of ultraviolet irradiation. Methyl vinyl siloxane with the molecular weight of about 30,000 and N- [ (2-mercaptoethyl) carbamoyl ] propionamide are used as raw materials, DMPA is used as a photoinitiator, and the siloxane (b) containing hydrogen bond groups is prepared by thiol-ene click reaction under the condition of ultraviolet irradiation. The diene double-end-capped siloxane is prepared by using hexadienol and hydroxyl siloxane with the molecular weight of about 500 as raw materials, controlling the molar ratio of the hexadienol and the hydroxyl siloxane to be 2: 1 and performing hydrolytic condensation.

Adding 5.7g of sodium tetraborate and 30g of hydroxyl-terminated polydimethylsiloxane with the molecular weight of about 20,000 into a dry and clean reaction bottle, adding a small amount of acetic acid aqueous solution, stirring and mixing for 30min, dropwise adding a small amount of BHT antioxidant, 3 wt% of tetramethylammonium hydroxide and 2 wt% of sodium glycerol, heating to 120 ℃, mixing for 30min, dropwise adding a small amount of triethylamine, reacting for 3h under the protection of nitrogen to obtain cross-linked polysiloxane, and cutting the cross-linked polysiloxane into particles with uniform size. Weighing 100 parts by weight of crosslinked polysiloxane particles, 400 parts by weight of water and 7 parts by weight of magnesium pyrophosphate, adding the crosslinked polysiloxane particles, adding 40 parts by weight of supercritical ethane into a high-pressure reaction kettle in a stirring state, heating the high-pressure reaction kettle to 120 ℃, keeping the pressure in the high-pressure kettle at 20bar, maintaining the high-pressure reaction kettle for 2 hours under the conditions of temperature and pressure, opening a discharge valve at the bottom end of the high-pressure kettle, taking out foam particles, washing and air-drying. Measuring a proper amount of hydrophilic ionic liquid [ BMIm]BF₄And adding 25 wt% of nano silicon dioxide into the mixture to obtain the dilatant dispersion liquid. Pressurizing and soaking the prepared polysiloxane foam particles in dilatant dispersion liquid for 2h, taking out the obtained polysiloxane foam particles, wiping off residual liquid on the surface, sintering the surface at a certain temperature,finally, polysiloxane foam particles with dilatancy are obtained.

200ml of THF is added into a three-neck flask, 20g of siloxane (a) containing disulfide ester side groups, 5.8g of diene double-end-blocked siloxane, 15g of siloxane (b) containing hydrogen bond groups and a proper amount of zinc chloride are added as catalysts, the mixture is heated to 50 ℃ and stirred to be dissolved, 1.2g of tetramethylammonium hydroxide and 0.8g of sodium glycerol are added to continue to react for 2 hours, then the mixture is stirred to react for 24 hours at 50 ℃, and then the sample is placed in a vacuum oven at 50 ℃ to obtain a dynamic polysiloxane sample with certain viscoelasticity.

Weighing 40 parts by weight of polysiloxane foam particles, 60 parts by weight of a dynamic polysiloxane sample, 2 parts by weight of talcum powder, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid, adding the materials into a small internal mixer for mixing for 10min, filling the premix into a proper mold, closing the mold, performing hot-press molding by using hot air, setting the mold temperature to be 90 ℃, the mold closing pressure to be 10Mpa, the mold pressing time to be 10min, then releasing the pressure, cooling and demolding to obtain a composite material, detecting the tensile strength and the elongation at break of the sample according to DIN EN ISO 1856 standard (wherein the experimental rate is 100mm/min), the tensile strength of the sample is 1.78MPa, the elongation at break is 265%, and detecting the resilience of the sample according to DIN53512 standard, wherein the resilience is 43%. The article (80X 20mm) was pressed by hand to 75% of its thickness, held for 60s and then slowly released, and the time required for the sample to return to the deformed position of 5% of its original thickness was measured and recorded as 10.74s on a stopwatch. The prepared composite material product has good dilatancy, the composite material can keep elasticity in a normal state, and shows temporary rigidity when being impacted, and returns to a normal elastic state after being impacted, and the impact resistance effect can be different along with the environmental change.

Example 40

DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercapto-1, 2, 4-triazole and hydroxyl-terminated polybutadiene are subjected to a thiol-ene click reaction to prepare the triazole grafted modified polybutadiene. Taking DMPA as a photoinitiator and ultraviolet light as a light source, and carrying out thiol-ene click reaction on 12-mercapto dodecyl phosphoric acid and hydroxyl-terminated polybutadiene to obtain the phosphoric acid grafted modified polybutadiene.

Adding 0.01mol of azole graft modified polybutadiene, 0.01mol of phosphoric acid graft modified polybutadiene, 0.02mol of trithiol compound (a) and 3mmol of 4-bromobenzenesulfonic acid butyl ester (b) into a dry and clean reaction bottle, uniformly stirring, adding 0.2 wt% of photoinitiator DMPA, stirring, fully mixing, placing in an ultraviolet crosslinking instrument for ultraviolet radiation for 4 hours, placing reactants into a proper mold, placing in a vacuum oven at 60 ℃ for 12 hours for further reaction and drying to obtain polybutadiene-based polymer, and cutting the polybutadiene-based polymer into particles with uniform size. Adding 90 parts by weight of polybutadiene-based polymer particles, 3 parts by weight of calcium carbonate, 1.5 parts by weight of silicon dioxide, 0.05 part by weight of antioxidant 168, 2 parts by weight of anti-aging agent 4010NA and 1 part by weight of stearic acid into a small internal mixer, mixing for 15min, adding into a charging barrel of a first extruder, heating and melting at 160 ℃, injecting supercritical nitrogen into the tail end of the first extruder, wherein the injection weight ratio of the materials to the supercritical nitrogen per hour is controlled at 100: 20, injecting the mixed polymer/high-pressure fluid melt into a second extruder through a melt pump, gradually cooling, uniformly mixing, extruding and foaming from a port die of the second extruder, and preparing the polybutadiene foam particles through underwater granulation.

Weighing 30g of polybutadiene foam particles, 30g of polybutadiene rubber (c), 3.0g of foaming agent AC, 1.5g of dimercapto compound (d), 1.0g of 1.0g N- [ (2-mercaptoethyl) carbamoyl ] propionamide, 0.12g of photoinitiator DMPA, 1.5g of zinc stearate, 1.5g of tribasic lead sulfate, 2g of self-carbon black, 0.05g of barium stearate, 0.1g of stearic acid, 0.1g of antioxidant 168 and 0.2g of antioxidant 1010, adding the mixture into a small internal mixer, mixing for 20min, filling the mixture into a proper mold, reacting for 15min under ultraviolet irradiation, closing the mold, setting the mold temperature at 150 ℃, the mold closing pressure at 10MPa, and the mold pressing time at 20min, then releasing the pressure, cooling and demolding to obtain a composite foam product, and detecting the resilience of a sample according to DIN53512 standard, wherein the resilience is 50%. The product has good overall flexibility and can compress and rebound. After the foam material is cut off by a blade, a certain pressure is applied to the cross section, the foam material is placed in a vacuum oven at the temperature of 60 ℃ for 4-5h, and the cross section can be bonded again. The foam material can be used as a recyclable shoe material filling material.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. A dynamic polymer foam composite comprising skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer comprises at least one dynamic covalent bond in the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

2. A dynamic polymer foam composite comprising skinned polymer foam particles and a dynamic polymer; wherein, the dynamic polymer contains at least one dynamic covalent bond and at least one supramolecular interaction on the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

3. A dynamic polymer foam composite comprising skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains at least two kinds of supramolecules on the polymer chain; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

4. The dynamic polymer foam composite of any one of claims 1 and 2, wherein the dynamic covalent bond is selected from the group consisting of boron-containing dynamic covalent bonds, dynamic sulfur bonds, dynamic selenium sulfur bonds, dynamic selenium nitrogen bonds, acetal dynamic covalent bonds, carbon-nitrogen double bond-based dynamic covalent bonds, reversible free radical-based dynamic covalent bonds, associative exchangeable acyl bonds, steric induced dynamic covalent bonds, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon-ether bonds, alkylazazonium-based exchangeable dynamic covalent bonds, olefin cross metathesis double bonds, alkyne cross metathesis triple bonds, 2+2 cycloaddition dynamic covalent bonds, 4+2 cycloaddition dynamic covalent bonds, alkyne cross metathesis double bonds, and combinations thereof, [4+4] cycloaddition dynamic covalent bond, mercapto-Michael addition dynamic covalent bond, amine alkene-Michael addition dynamic covalent bond, triazolinedione-indole-based dynamic covalent bond, diazacarbene-based dynamic covalent bond, benzoyl-based dynamic covalent bond, hexahydrotriazine-based dynamic covalent bond, dynamic exchangeable trialkylsulfonium bond, dynamic acid ester bond, diketoenamine dynamic covalent bond.

5. The dynamic polymer foam composite of any of claims 2 and 3, wherein the supramolecular interaction is selected from the group consisting of metal-ligand interaction, hydrogen bonding, halogen bonding, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction (positive and negative ion pair interaction), ionic clustering interaction, ion-dipole interaction, dipole-dipole interaction, metallophilic interaction, ionic hydrogen bonding interaction, radical cation dimerization, Lewis acid-base pair interaction, host-guest interaction, phase separation, crystallization.

6. The dynamic polymer foam composite according to any of claims 1 to 3, wherein the skinned polymer foam particles have a dilatancy which is achieved by using an intrinsically dilatant polymer as the polymer matrix to give the foam particles dilatancy or by blending an intrinsically dilatant polymer component and/or a dispersive dilatant component and/or an aerodynamic dilatant structure in the polymer matrix to give the foam particles dilatancy.

7. The dynamic polymer foam composite according to any of claims 1 to 3, characterized in that the skinned polymer foam particles are dynamic by covalent bonding of dynamic covalent bonds and/or supramolecular interactions in the expandable polymer (composition) or expandable polymer precursor (composition).

8. The dynamic polymer foam composite according to any of claims 1 to 3, characterized in that the skinned polymer foam particles are force-responsive by covalently attaching force-sensitive groups and/or physically blending force-responsive components in the expandable polymer (composition) or expandable polymer precursor (composition).

9. The dynamic polymer foam composite according to any of claims 1 to 3, characterized in that the dynamic polymer and its polymer composition with optional components is foamed.

10. A dynamic polymer foam composite comprising skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains one of the following supermolecule actions on the polymer chain: metal-ligand interaction, halogen bond interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic interaction (positive and negative ion pair interaction), ion cluster interaction, ion-dipole interaction, dipole-dipole interaction, metallophilic interaction, ionic hydrogen bonding interaction, radical cation dimerization, lewis acid-base pair interaction, host-guest interaction, phase separation, crystallization; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

11. A dynamic polymer foam composite comprising skinned polymer foam particles and a dynamic polymer; wherein the dynamic polymer contains at least one hydrogen bonding group of the following structural components on the polymer chain:

wherein W is selected from oxygen atom and sulfur atom; x is selected from sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from sulfur atoms, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atom, heteroatom group, small molecule alkyl and polymer chain residue; i is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small molecule hydrocarbon group; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small molecule hydrocarbon group; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, and at least two ring-forming atoms are nitrogen atoms; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom, or other hetero atom; wherein, the skinned polymer foam particles are prepared by directly foaming and/or 3D printing an expandable polymer (composition) or an expandable polymer precursor (composition), and have a skin structure; wherein the skinned polymeric foam particles are compounded with the dynamic polymer and other optional components to form the composite.

12. The dynamic polymer foam composite according to any one of claims 1 to 3, 10 or 11, which is applied to the production of foam parts in packaging materials, construction materials, impact protection materials, shock absorbing materials, cushioning materials, sound absorbing materials, thermal materials, shape memory materials, electronic and electrical materials, medical supplies, helmet shells, body protectors, footwear products, sports protective products, military and police protective products, automobile bumpers, automobile interior trim parts, vehicle seats, cushioning pads, body building protection parts, floor covering materials.

13. A preparation method of a dynamic polymer foam composite material is characterized in that a composite material product is prepared by premixing skinned polymer foam particles or polymer particles to be foamed, a dynamic polymer or raw materials thereof, an optional foaming agent, optional other auxiliary agents and optional fillers, filling the premixed materials into a proper mold, and performing hot press molding under certain temperature and pressure conditions.