CN111253583B - Dilatant hybrid dynamic polymer and dilatant realization method thereof - Google Patents

Abstract

The invention relates to a dilatant hybrid dynamic polymer which at least contains vitrification dilatant and common covalent cross-linking above gel point and contains dynamic units. The dilatant hybrid dynamic polymer has excellent dilatant, wherein common covalent crosslinking provides good structural stability for the polymer, and dynamic units have dynamic reversibility, so that the polymer is provided with synergistic dilatant, molecular-level and microcosmic self-repairing performance and shape memory performance, and the strength, toughness and damage resistance of the material are improved. The dilatant hybrid dynamic polymer can be used as an energy absorbing material, a ductile material, a shape memory material and the like, and is widely applied to shock resistance protection, shock absorption, damping, sound absorption, noise elimination, packaging, medical treatment, traffic and the like. The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer and an energy absorption method for absorbing energy by taking the dilatancy hybrid dynamic polymer as an energy absorption material.

Description

Dilatant hybrid dynamic polymer and dilatant realization method thereof

Technical Field

The invention relates to a dilatant hybrid dynamic polymer, a dilatant realization method thereof and an energy absorption method for absorbing energy by taking the dilatant hybrid dynamic polymer as an energy absorption material.

Background

The polymer material/polymer material is a material which is a later-developed material compared with the traditional materials such as cement, glass, ceramic and metal, but the development speed and the application universality of the polymer material/polymer material are greatly superior to those of the traditional materials, and the polymer material/polymer material plays an increasingly important role in various fields such as daily life, industry, agriculture, national defense, military, science and technology and the like. The polymer material has excellent processability such as plasticity, ductility, extrudability, spinnability, etc. The advantages of polymeric materials are also reflected in their high elastic, low elastic modulus, viscoelastic and other mechanical properties, which make polymeric materials, especially polymeric elastomers and foams, often used as protective materials, such as damping materials, cushioning materials, and shock absorbing/shock absorbing materials. However, conventional polymer elastomers and foams are often only highly resilient or plastic due to their single structural component and insufficient properties. When the high-elasticity polymer material is impacted by energy, the contact area can be increased only through the deformation of the foam, so that the purpose of dispersing impact energy is achieved, but the impact energy absorption and loss effect is limited, so that the energy absorption and protection essence of the traditional polymer protection material is to damp and buffer in a temporary energy storage mode, and the problems of single energy absorption mechanism, unsatisfactory energy absorption effect and the like exist. In addition, due to the high elasticity of the traditional polymer elastomer and the foam, the traditional polymer elastomer and the foam are easy to cause secondary injury of a protection object in the process of instantaneously releasing a large amount of stored energy in an energy absorption application scene. The plastic deformation of the fully plastic polymer material can absorb a small amount of impact energy under the impact of energy, but the current situation cannot be recovered again, so that the problems of limited energy absorption times, short service life and the like are caused.

Therefore, the traditional polymer material has a single energy absorption mechanism and a very limited energy absorption effect, and the polymer can not absorb and consume impact energy through the increase of viscosity and/or strength and/or hardness under the action of shearing force or other mechanical external force, namely, the energy absorption can not be carried out through the dilatancy of the polymer.

The crosslinking of the polymer is an important factor in achieving good mechanical strength and structural stability. Conventional crosslinked polymeric materials are typically thermoset materials, lacking reversible, sacrificial components, on the one hand the crosslinked materials are not sufficiently resistant to failure; on the other hand, after the structure of the crosslinked polymer material is damaged, the damage repair is difficult to carry out no matter in molecular level, microcosmic or macroscopic, and the material is easy to be unusable due to the overall catastrophic damage after the internal partial damage of the polymer material, so that the service life is short and the serious resource waste is caused. The performance deficiencies of conventional polymeric materials are also manifested by difficulties in custom production and use depending on the application scenario.

Therefore, there is a need to develop a novel hybrid dynamic polymer and a method for realizing the dilatancy of the hybrid dynamic polymer, so as to obtain a dilatancy hybrid dynamic polymer elastomer, a dilatancy hybrid dynamic polymer gel and a dilatancy hybrid dynamic polymer foam which have good dilatancy and excellent anti-damage capability and can self-repair at molecular level and microscopic level, etc., so as to solve the problems in the prior art.

Disclosure of Invention

The invention aims at the background and provides a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent crosslinking above a gel point and dynamic units. The dilatant hybrid dynamic polymer has excellent dilatant, wherein common covalent crosslinking provides good structural stability for the polymer, and dynamic units have dynamic reversibility, so that the polymer is provided with synergistic dilatant, molecular-level and microcosmic self-repairing performance and shape memory performance, and the strength, toughness and damage resistance of the material are improved. The dilatant hybrid dynamic polymer can be used as an energy absorbing material, a ductile material, a shape memory material and the like, and is widely applied to shock resistance, protection, shock absorption, damping, sound absorption, noise elimination, packaging, medical treatment, traffic and the like. The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer and an energy absorption method for absorbing energy by taking the dilatancy hybrid dynamic polymer as an energy absorption material.

The invention is realized by the following technical scheme:

the invention relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bond and non-covalent function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the dynamic covalent bond and the non-covalent effect above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bond and non-covalent function.

In the present invention, the dilatant hybrid dynamic polymer may be an unfoamed solid (including gel) or a foamed foam.

In the present invention, the dilatant hybrid dynamic polymer contains at least vitrified dilatant, which means that the dilatant hybrid dynamic polymer may contain vitrified dilatant alone or may contain a combination of two or more different ways including vitrified dilatant, i.e. the dilatant hybrid dynamic polymer of the present invention contains vitrified dilatant and optionally at least one dilatant selected from dynamic dilatant, entanglement dilatant, dispersive dilatant and pneumatic dilatant. More specifically, the dilatant hybrid dynamic polymer optionally contains dynamic dilatant based on the contained vitrified dilatant polymer component, entanglement dilatant based on the dynamic dilatant polymer component, dispersive dilatant based on the dispersive dilatant composition and aerodynamic dilatant based on the aerodynamic dilatant structure in addition to vitrified dilatant based on the contained vitrified dilatant polymer component, further enriching dilatant, and cooperativity and/or orthogonality thereof.

In embodiments of the present invention, when two or more dilatant including vitrification dilatant are included in the dilatant hybrid dynamic polymer, it includes, but is not limited to, the method comprises the steps of physical mixing of vitrified dilatant and dynamic dilatant, physical mixing of vitrified dilatant and entanglement dilatant, physical mixing of vitrified dilatant and dispersive dilatant, physical mixing of vitrified dilatant and dynamic dilatant and entanglement dilatant, physical mixing of vitrified dilatant and dynamic dilatant and pneumatic dilatant, physical mixing of vitrified dilatant and dispersive dilatant and pneumatic dilatant, chemical hybridization forms of vitrified dilatant and dynamic dilatant on polymer chains, and chemical hybridization forms of vitrified dilatant and dynamic dilatant on polymer chains.

In the present invention, the glassy dilatant may be obtained by incorporating in the polymer a glassy dilatant polymer composition, which refers to a polymer segment (also including oligomer segments, hereinafter also referred to as such) having at least one glass transition temperature, preferably at least one polymer segment having a glass transition temperature in the range of-40 ℃ to 60 ℃, which may be a soft segment and/or a cross-linking point segment of the dilatant polymer. The vitreous dilatant polymer component described in the present invention may be chemically linked to the linking segments of the dilatant polymer cross-linked network polymer chains as cross-linked network or may be dispersed in the cross-linked network in a physically blended form, preferably introduced into the cross-linked network polymer chains in a chemically linked form, to obtain a dilatant process of greater reliability and stability.

In a preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has only one glass transition temperature, the glass transition temperature being in the range of-40 ℃ to 60 ℃; preferably at-10 to 40 ℃.

In another preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has at least two glass transition temperatures, one of which is between-60 ℃ and 0 ℃, preferably between-40 ℃ and 0 ℃; the other glass transition temperature is between 0 ℃ and 80 ℃, preferably between 0 ℃ and 40 ℃; preferably, the two glass transition temperatures have an overlap.

In another preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has at least two glass transition temperatures, one of which is between-40 ℃ and 60 ℃, preferably between-10 ℃ and 40 ℃; the other glass transition temperature is between-100 ℃ and-40 ℃; preferably at-80℃to-50 ℃.

In an embodiment of the present invention, the glassy dilatant polymer component contained in the dilatant hybrid dynamic polymer may be dispersed in a non-glassy dilatant polymer cross-linked network of dilatant polymer in a non-cross-linked form providing glassy dilatant; the vitrification dilatant polymer component can be crosslinked by one or more structures of a common covalent bond, a weak dynamic non-covalent bond, a strong dynamic covalent bond and a strong dynamic non-covalent bond, and is introduced into a polymer to provide vitrification dilatant; the same or different non-crosslinked glassy dilatant polymer components may also be dispersed in a polymer crosslinked network having glassy dilatant properties to collectively provide glassy dilatant properties. The present invention also does not exclude non-crosslinked glassy dilatant polymer components as dilatant hybrid dynamic polymers according to the present invention.

In the invention, the vitrification dilatant caused by the glass transition temperature of the polymer has the characteristic of strong adjustability of the working temperature range, and is convenient for obtaining dilatant materials with specific working temperature ranges.

In the present invention, a dynamic dilatant polymer composition refers to a polymer (including oligomer) comprising at least one strongly dynamic non-covalent and/or strongly dynamic covalent bond.

In embodiments of the present invention, typical strong dynamic non-covalent interactions include, but are not limited to: mono-dentate hydrogen bonding, di-dentate hydrogen bonding, mono-dentate metal-ligand bonding, di-dentate metal-ligand bonding, ionic-dipole bonding, host-guest bonding, metalphilic bonding, dipole-dipole bonding, halogen bonding, lewis acid base pairing, cation-pi bonding, anion-pi bonding, benzene-fluorobenzene bonding, pi-pi stacking, ionic hydrogen bonding, free radical cation dimerization; typical highly dynamic covalent bonds include, but are not limited to: boron-containing dynamic covalent bonds, dynamic covalent bonds of metal acid esters, and dynamic covalent bonds based on reversible free radicals. Among them, preferred is a monodentate hydrogen bonding action, a bidentate hydrogen bonding action, a monodentate metal-ligand action, an ion cluster action, an ion-dipole action, a host-guest action, a Lewis acid-base pair action, an ion hydrogen bonding action, an inorganic boric acid monoester bond, a saturated five-membered ring inorganic boric acid ester bond, an unsaturated five-membered ring inorganic boric acid ester bond, an organic boric acid monoester bond, a saturated five-membered ring organic boric acid ester bond, an unsaturated five-membered ring organic boric acid ester bond, a saturated six-membered ring organic boric acid ester bond, an unsaturated six-membered ring organic boric acid ester bond (especially a saturated five-membered ring organic boric acid ester bond/an unsaturated six-membered ring organic boric acid ester bond) to which aminomethyl phenyl groups are bonded, an inorganic boric acid silicone ester bond, an organic boric acid silicone ester bond, a dynamic silicon titanate ester bond, more preferably, the one-tooth hydrogen bonding, the two-tooth hydrogen bonding, the one-tooth metal-ligand bonding, the ion-dipole bonding, the host-guest bonding, the ion bonding, the inorganic boric acid monoester bond, the organic boric acid monoester bond, the saturated five-membered ring organic boric acid ester bond with aminomethyl phenyl group, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond, the unsaturated six-membered ring organic boric acid ester bond, the inorganic boric acid silicone ester bond, the organic boric acid silicone ester bond and the dynamic titanic acid silicone ester bond are high in dynamic property and good in regulation and control performance.

In the invention, dynamic dilatancy caused by strong dynamic non-covalent action and/or dynamic covalent bond has the characteristics of rich regulation means, high dynamic transformation speed and the like. In the embodiment of the invention, by designing and selecting proper dynamic dilatant polymer components, various combined dilatant containing dynamic dilatant can be effectively designed and regulated, and excellent comprehensive dilatant can be obtained.

In an embodiment of the present invention, the dynamic dilatant polymer component contained in the dilatant hybrid dynamic polymer, which can be dispersed in a non-crosslinked form in a crosslinked network of polymers having vitrification dilatant properties, provides the dilatant polymer with dynamic dilatant properties; the dynamic dilatant polymer component can be crosslinked by the contained strong dynamic covalent bond and/or strong dynamic noncovalent action to form a polymer crosslinked network with dynamic dilatant property, so as to provide dynamic dilatant property, and the vitrified dilatant polymer component is crosslinked by the strong dynamic covalent bond and/or strong dynamic noncovalent action to provide dynamic dilatant property; the dynamic dilatant polymer component can be crosslinked by the contained strong dynamic covalent bond and/or strong dynamic non-covalent action to form a polymer crosslinked network with dynamic dilatant, and then the polymer crosslinked network with vitrification dilatant is combined together in a physical dispersion mode, an interpenetrating mode, a partially interpenetrating mode or the like to provide the dynamic dilatant. In the embodiment of the invention, a strong dynamic covalent bond and/or a strong dynamic non-covalent effect can be introduced into a polymer crosslinked network with vitrification dilatant to obtain a dynamic dilatant polymer component and provide dynamic dilatant.

In the present invention, the entangled dilatant polymer component means a polymer component capable of achieving dilatancy by entanglement of polymer molecular chains such that the polymer chains cannot move in time when subjected to shear. In embodiments of the present invention, it is preferred that the molecular chains of the entangled dilatant polymer have a glass transition temperature of not higher than-20 ℃, more preferably not higher than-40 ℃, more preferably not higher than-60 ℃, more preferably not higher than-100 ℃. In an embodiment of the invention, the molecular weight of the entangled dilatant polymer needs to be high enough to obtain the entanglement effect under shear, preferably not lower than 100kDa, more preferably not lower than 1000kDa.

In an embodiment of the present invention, the entangled dilatant polymer component contained in the dilatant hybrid dynamic polymer, which can be dispersed in a non-crosslinked form in a crosslinked network of a polymer having vitrification dilatant properties, provides the dilatant polymer with entangled dilatant properties; the entangled dilatant polymer composition may also be covalently or non-covalently linked to the cross-linked network in the form of side chains, terminal chains, providing entangled dilatancy.

In the present invention, the dispersible dilatant composition contains at least 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%, still more preferably not less than 40%.

In the present invention, the dispersible dilatant composition is preferably swollen or dispersed in a polymer network (including a polymer cross-linked network having a vitrifiable dilatant); or by coating, dipping, etc. in a self-supporting porous, hollow polymeric material (including vitrified dilatant polymers).

In the invention, the solid microparticles and the dispersion liquid/dispersion needed for realizing the dispersibility dilatant have rich commercial sources, the dispersion process does not need to carry out complex chemical reaction, and the invention has the characteristic of high performance controllability. The dispersion of inorganic particles also has the characteristic of puncture resistance.

In the invention, when the form of the dilatant hybrid dynamic polymer is foam, the rebound time is increased and the dilatant is enhanced by controlling the open cell structure of the foam, generally when the open cell surface area ratio is reduced. In order to obtain a suitable dilatancy, the ratio of open area to cell surface area is preferably 3% to 20%, more preferably 5% to 15%, still more preferably 5% to 10%.

In the present invention, the cell structure with partial opening is considered as a gas-dynamic dilatant structure.

In the invention, the pneumatic dilatant has the characteristic of insensitive temperature, is convenient for keeping relatively stable dilatant performance in a wider temperature range, and the partially open cell structure can reduce the shrinkage rate of the foam after cooling and improve the molding stability of the dilatant foam.

In the invention, the dilatant hybrid dynamic polymer is of a crosslinked structure, namely the dilatant hybrid dynamic polymer at least comprises a crosslinked network, the crosslinking degree of common covalent crosslinking in the crosslinked network is above a gel point, continuous structural stability and excellent mechanical property are provided for the polymer, the continuous structural stability can be provided in the dynamic reversible transformation process of the contained dynamic covalent bond and/or non-covalent action, the disintegration of the material is avoided, and the structural stability and the use safety of the dilatant material can be greatly improved. Wherein, the cross-linked structure can be dispersed or blended with a non-cross-linked structure.

In the invention, the dilatant hybrid dynamic polymer contains dynamic covalent crosslinking and non-covalent crosslinking, so that dynamic covalent and non-covalent dynamic properties can be obtained, and richer dynamic stimulus responsiveness can be realized. Based on the dynamic reversibility of the contained dynamic crosslinking, the molecular level and microcosmic self-repairing performance can be provided for the polymer, and the polymer can also be used as a sacrificial bond for absorbing energy, improving toughness and improving damage resistance. In particular, a weak dynamic cross-linking above the gel point is introduced into the polymer, which can also provide a shape memory function to the polymer together with a common covalent cross-linking; the high dynamic cross-linking is introduced into the polymer, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In the invention, the dynamic units (namely the dynamic covalent bond and the non-covalent function) contained in the dilatant hybrid dynamic polymer preferably have a crosslinking function so as to improve the mechanical property, dilatant property, self-repairing property and comprehensive energy absorption property of the material.

In the present invention, the dilatant hybrid dynamic polymer may contain only one crosslinked network (single network structure) or may contain at least two crosslinked networks (multi-network structure).

In the invention, the dilatant hybrid dynamic polymer with a single network structure can be a common covalent cross-linked network and a hybrid cross-linked network, wherein the degree of cross-linking of the common covalent cross-linked in the cross-linked network is above a gel point; the single network structure contains at least one vitrified dilatant polymer component to obtain vitrified dilatant. The single network structure may optionally further comprise dynamic dilatant based on a dynamic dilatant polymer composition, entanglement dilatant based on an entanglement dilatant polymer composition, dispersive dilatant based on a dispersive dilatant composition, and aerodynamic dilatant based on an aerodynamic dilatant structure to enrich dilatant of the dilatant polymer.

In the present invention, the dilatant hybrid dynamic polymer having a multi-network structure may be formed by blending two or more cross-linked networks, may be formed by interpenetration of two or more cross-linked network portions, or may be formed by combination of three or more cross-linked networks, but the present invention is not limited thereto. In the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance.

In the invention, the dilatant hybrid dynamic polymer with the multi-network structure comprises at least one crosslinked network which contains a vitrified dilatant polymer component so as to obtain vitrified dilatant, and preferably each crosslinked network has the vitrified dilatant polymer component; the vitreous dilatant polymer component in each crosslinked network may be the same or different. The partially or fully crosslinked network of the dilatant hybrid dynamic polymer with the multi-network structure also optionally contains dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant components and pneumatic dilatant based on pneumatic dilatant structures so as to enrich dilatant of the dilatant polymer.

In the invention, the mechanical property, the dilatant property, the dynamic property and other using properties of the polymer can be regulated and controlled by reasonably designing the dilatant hybrid dynamic polymer crosslinked network structure.

In an embodiment of the present invention, the non-crosslinked structure dispersed or blended in the crosslinked network of the dilatant hybrid dynamic polymer is preferably a non-crosslinked dilatant polymer, more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic covalent bond and/or strong dynamic non-covalent effect, which facilitates obtaining additional dynamic dilatant, and also facilitates viscous flow through its segments, further enhancing energy absorbing properties.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has a very rich energy absorbing mechanism, except the traditional energy absorbing mechanism, the energy absorbing method also comprises the steps of carrying out energy absorption through the dilatancy of the polymer, carrying out energy absorption through dynamic covalent bonds and non-covalent action in the polymer and dynamic reversible transformation processes, and the like as sacrificial bonds, so that the energy absorbing method can provide excellent energy absorbing performance for the polymer energy absorbing material and carry out effective energy absorbing and impact resisting protection, thereby solving the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

In the present invention, the dynamic covalent bond includes a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond. Wherein the boron-containing dynamic covalent bond comprises, but is not limited to, an organic boron anhydride bond, an inorganic boron anhydride bond, an organic-inorganic boron anhydride bond, a saturated five-membered ring organic boric acid ester bond, an unsaturated five-membered ring organic boric acid ester bond, a saturated six-membered ring organic boric acid ester bond, an unsaturated six-membered ring organic boric acid ester bond, a saturated five-membered ring inorganic boric acid ester bond, an unsaturated five-membered ring inorganic boric acid ester bond, a saturated six-membered ring inorganic boric acid ester bond, an unsaturated six-membered ring inorganic boric acid ester bond, an organic boric acid monoester bond, an inorganic boric acid monoester bond, an organic boric acid silicon ester bond and an inorganic boric acid silicon ester bond. Wherein the boron-free dynamic covalent bond comprises, but is not limited to, a dynamic continuous sulfur bond, a dynamic continuous selenium bond, a dynamic selenium sulfur bond, a dynamic selenium nitrogen bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on reversible free radicals, a cohesive exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a dynamic reversible addition fragmentation chain transfer covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyl nitrogen heterocyclic onium, an unsaturated carbon-carbon double bond capable of generating alkene cross metathesis reaction, an unsaturated carbon-carbon triple bond capable of generating alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond, mercapto-Michael addition dynamic covalent bond, an amine-Michael addition dynamic covalent bond, a dynamic covalent bond based on triazolin dione-indole, a dynamic covalent bond based on diazacarbene, a dynamic covalent bond based on benzoyl, a hexahydrotriazine dynamic covalent bond, a dynamic exchangeable trialkylsulfonium bond, a dynamic ketene bond, and a dynamic amine ester bond.

In the invention, dynamic covalent crosslinking is used as a covalent crosslinking structure, so that good stability can be provided, and the effects of stabilizing the balance structure and providing good mechanical strength can be achieved; the polymer material can show dynamic covalent property and dynamic reversibility under specific conditions, so that molecular-level and microscopic self-repairing performance can be realized through dynamic reversibility of dynamic covalent crosslinking when local structural damage occurs to the polymer material. Different kinds of dynamic covalent bonds are introduced into the polymer, so that the polymer can show different response effects to external stimuli such as heat, illumination, pH, redox agents and the like, and the dynamic reversible balance can be promoted or slowed down under proper environment by selectively controlling the external conditions, so that the polymer is in a required state. The dynamic covalent bond, especially the weak dynamic covalent bond, can also be used as a sacrificial bond to absorb impact energy and improve toughness and damage resistance; the strong dynamic covalent bond can also be the dynamic dilatant of the polymer and improve the tear resistance of the material.

In the present invention, the non-covalent interactions include supramolecular interactions, phase separation and crystallization; the supermolecular interactions include hydrogen bonding interactions and non-hydrogen bonding supermolecular interactions, wherein the non-hydrogen bonding supermolecular interactions include, but are not limited to, at least one of the following: metal-ligand action, ion cluster action, ion-dipole action, host-guest action, metallophilic action, dipole-dipole action, halogen bond action, lewis acid base pair action, cation-pi action, anion-pi action, benzene-fluorobenzene action, pi-pi stacking action, ion hydrogen bonding action, free radical cation dimerization action.

In the invention, the weak dynamic non-covalent crosslinking generally has higher bonding strength, so that the mechanical strength and modulus of the material are conveniently improved, and the weak dynamic non-covalent crosslinking can be used as a sacrificial bond to absorb impact energy, improve toughness and improve damage resistance. The strong dynamic non-covalent crosslinking has the advantages that the exchange speed is high, and non-covalent motifs at different positions can be exchanged and recombined, so that more excellent dynamic dilatant performance is obtained, the low-temperature hardening process of the dilatant polymer can be effectively inhibited, the sensitivity of the dilatant to temperature is reduced, the positive effect on the dilatant performance at low temperature is achieved, and the microcosmic self-repairing process of the material and the tear resistance of the material can be accelerated.

In embodiments of the present invention, typical weakly dynamic covalent bonds include, but are not limited to: dynamic continuous sulfur bond, dynamic continuous selenium bond, dynamic selenium sulfur bond, dynamic selenium nitrogen bond, acetal dynamic covalent bond, dynamic covalent bond based on carbon-nitrogen double bond, combined exchangeable acyl bond, dynamic covalent bond based on steric effect induction, 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 generating alkene cross metathesis reaction, unsaturated carbon triple bond capable of generating alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond, mercapto-Michael addition dynamic covalent bond, amine alkene-Michael addition dynamic covalent bond, dynamic covalent bond based on triazoline diketone-indole, dynamic covalent bond based on diazacarbene, benzoyl-based dynamic covalent bond, hexahydrotriazine dynamic exchangeable trialkylsulfonium bond, dynamic covalent bond of diketone enamine.

In embodiments of the present invention, typical weak dynamic non-covalent interactions include, but are not limited to: hydrogen bonding, metal-ligand, phase separation, crystallization of three or more teeth.

In the invention, two or more dynamic units, especially dynamic units with different stimulus responsivity/dynamic reversible conditions, are introduced into the dilatant hybrid dynamic polymer, so that the dynamic performance with orthogonality and multiple stimulus responsivity can be obtained, and the shape memory function can be obtained.

In the embodiment of the invention, the dilatant hybrid dynamic polymer can be uniform or have a gradual structure/gradient structure, so that the mechanical property with gradual change/gradient change is obtained to adapt to the requirements of different application scenes.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bonds.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the dynamic covalent bond above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bonds.

In a preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from boron-containing dynamic covalent bonds.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from boron-free dynamic covalent bonds.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from dynamic covalent bonds based on reversible free radicals.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from dynamic acid ester linkages.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from the group consisting of dynamic sulfide bonds, dynamic selenium sulfide bonds, reversible addition fragmentation chain transfer dynamic covalent bonds, thiol-michael addition dynamic covalent bonds, amine alkene-michael addition dynamic covalent bonds.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from the group consisting of [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond and [4+4] cycloaddition dynamic covalent bond.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a dynamic covalent bond comprising boron and a dynamic covalent bond comprising no boron.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond, wherein the boron-free dynamic covalent bond has a strong dynamic property.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond, wherein the boron-free dynamic covalent bond has a weak dynamic property.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises at least two dynamic covalent bonds, preferably the dynamic covalent bonds have orthogonal dynamics.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that the degree of crosslinking of the ordinary covalent crosslinks in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the non-hydrogen bond supermolecular action above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function.

Non-hydrogen bond supramolecular interactions as described herein refer to supramolecular interactions other than hydrogen bonding, which include, but are not limited to, metal-ligand interactions, ionic interactions, ion-cluster interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bond interactions, lewis acid base pairing interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ion hydrogen bonding interactions, radical cation dimerization interactions.

In a preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises bidentate and below metal-ligand interactions.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises tridentate and more metal-ligand interactions.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a combination of bidentate and less bidentate metal-ligand interactions with tridentate and more tridentate metal-ligand interactions.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises ionic interactions.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a host-guest effect.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises lewis acid base pairs.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises pi-pi stacking.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a benzene-fluorobenzene action.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer contains halogen linkages.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a cation-pi-effect or an anion-pi-effect.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metallophilic interaction or a free radical cationic dimerization.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises at least two non-hydrogen bonding supramolecular interactions and at least one of the non-hydrogen bonding supramolecular interactions is a metal-ligand interaction, preferably the metal-ligand interaction is a tridentate or more metal-ligand interaction.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function and hydrogen bond function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the non-hydrogen bond supermolecular action and the hydrogen bond action above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function and hydrogen bond function.

In a preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a metal-ligand interaction and a hydrogen bonding interaction.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises ionic and hydrogen bonding.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises host-guest interactions and hydrogen bonding interactions.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises halogen bonding and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises lewis acid base pairing and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises benzene-fluorobenzene action and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect of three or more teeth and hydrogen bonding effect of two or less teeth.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises metal-ligand interactions of two or less teeth and hydrogen bonding interactions of three or more teeth.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises metal-ligand interactions with and hydrogen bonding interactions with bidentate and bidentate-less teeth.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect of three or more teeth and hydrogen bonding effect of three or more teeth.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action, wherein the hydrogen bond action is selected from hydrogen bond action of two teeth and teeth below, and hydrogen bond groups used for forming the hydrogen bond action of the teeth below are selected from at least one of the following structural components:

wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the hydrogen bonding effect above the gel point are simultaneously introduced to obtain the vitrification dilatancy and the optionally dynamic dilatancy; wherein the hydrogen bonding is selected from the hydrogen bonding of the number of teeth below two teeth, and the hydrogen bonding group used for forming the hydrogen bonding of the number of teeth below two teeth is selected from at least one of the following structural components:

Wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action, wherein the hydrogen bond action is selected from hydrogen bond action of two teeth and teeth below, and hydrogen bond groups used for forming the hydrogen bond action of the teeth below are selected from at least one of the following structural components:

wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action of the number of teeth above three teeth.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking above the gel point and the hydrogen bonding effect of the teeth number above the tridentate are introduced at the same time, so that the vitrification dilatancy and the dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action of the number of teeth above three teeth.

In the embodiment of the present invention, the hydrogen bond group for forming the hydrogen bond action with the number of teeth of three or more teeth may be present only on the polymer chain skeleton, only on the polymer chain side group, only on the polymer chain skeleton/end group of the small molecule, or may be present simultaneously on at least two of the polymer chain skeleton, the side group and the end group.

The dilatant hybrid dynamic polymer contains hydrogen bond action of the number of teeth of two teeth and below two teeth in addition to the hydrogen bond action of the number of teeth of three teeth and above three teeth so as to enrich non-covalent dynamic property of the material and obtain dynamic dilatant property. In the embodiment of the invention, the combination of the hydrogen bonding action of the three teeth and more teeth and the hydrogen bonding action of the two teeth and less teeth can better balance the mechanical property, the dynamic dilatancy, the microscopic self-repairing property and the like of the material.

In an embodiment of the present invention, the formulation components for preparing the dilatant hybrid dynamic polymer may further comprise any one or more of the following additives or usable substances: auxiliary agent, filler and swelling agent. The auxiliary agent is selected from any one or more of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, compatibilizers, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, matting agents, phase change additives, antistatic agents, dehydrating agents, sterilizing mildewcides, blowing agents, auxiliary blowing agents, nucleating agents, rheology agents; the filler is selected from any one or more of the following: inorganic nonmetallic fillers, metallic fillers, organic fillers, organometallic compound fillers; the swelling agent is selected from any one or more of the following: water, organic solvent, ionic liquid, oligomer and plasticizer.

In embodiments of the present invention, the dilatant hybrid dynamic polymer may be in the form of a gel (including hydrogels, organogels, oligomer-swollen gels, plasticizer-swollen gels, ionic liquid-swollen gels), elastomer, foam, or the like.

In embodiments of the present invention, the dilatant hybrid dynamic polymer is applicable to the following materials or articles: energy absorbing materials, tough materials, shape memory materials.

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

(1) In the invention, the dilatant hybrid dynamic polymer at least contains vitrification dilatant, which contains common covalent crosslinking above crosslinking points, dynamic covalent bonds and non-covalent (supermolecule) actions. The ordinary covalent crosslinking gives the material the structural balance and stability, wherein the vitrification dilatant component can be chemical structural components existing in the ordinary covalent crosslinking network structure or other network and/or non-network structures, or can be physical blending components dispersed in the ordinary covalent crosslinking network and/or non-network structures, and is preferably ordinary covalent crosslinking and/or dynamic covalent crosslinking and/or chemical structural components in the supermolecule crosslinking network structure. The dynamic covalent bond and the non-covalent effect may or may not be in the structure or component in which the dilatant component is located.

The vitrification dilatancy of the invention has the characteristic of wide-range adjustability. By reasonably regulating and controlling the glass transition temperature of the dilatant polymer, the dilatant polymer material has stable vitrification dilatant in a single temperature (narrow temperature range), a plurality of temperatures or a wide temperature range, and can better adapt to the requirements of application scenes at different temperatures on dilatant performance. For example, a dilatant polymer material having a single glass transition temperature and a small glass transition temperature span has a high sensitivity to temperature and shows a good temperature responsiveness and reliability; as another example, a dilatant polymer material having multiple glass transition temperatures, which is capable of having dilatancy at multiple temperature points/temperature intervals, can better accommodate application scenarios that require use at multiple different temperatures at the same time; as another example, the dilatant polymer material with a wider glass transition temperature span can play an effective energy absorbing role from extremely low temperature in winter to high temperature in desert in summer. Particularly, when the dilatant polymer material with dilatant property near room temperature can be used as protective headrests, seat filling materials, mattresses, shoe materials, sports protective mats, protective auto parts and other products, the dilatant polymer material can better relieve the pressure and fatigue of various parts of the body and provide better energy-absorbing protective effects, and is also helpful for obtaining room temperature slow rebound resilience, so that the problem of secondary injury of protective personnel and protective articles caused by the high-speed rebound process after the impact of the traditional energy-absorbing material is avoided; the dilatant polymer material with dilatant at room temperature and low temperature can effectively avoid the problems of material hardening and dilatant loss at low temperature, so that the dilatant polymer material can still effectively absorb energy at low temperature, and is better suitable for application scenes of low temperature even very low use temperature; meanwhile, the dilatant polymer material with glass transition temperature near room temperature and at middle and high temperature can not only keep stable dilatant at room temperature, but also avoid the problems of reduced material support and rapid decline or even complete loss of dilatant when the temperature is increased, and improve the practicability and reliability of the dilatant polymer material; the dilatant polymer materials with glass transition temperatures at low temperature, room temperature and medium and high temperature can realize dilatant in a wider temperature range, and can be better suitable for harsher application scenes of the dilatant polymer materials. The vitrification dilatancy is combined with at least one common covalent crosslinking network to achieve structural balance and stability well. These represent the practical effects that can be produced by the structure and performance characteristics of the dilatant hybrid dynamic polymer of the present invention, as well as the novelty and creativity of the dilatant hybrid dynamic polymer structure of the present invention and of the method of achieving dilatancy of said polymer.

In the present invention, the dynamic covalent bonds and non-covalent interactions contained therein, which impart the dynamic properties to the hybrid dynamic polymer, can be embodied in a number of ways. Including but not limited to sacrificial, microscopic self-healing, shape memory, dynamic dilatancy. The sacrificed property can provide additional toughness, even bionic super toughness, for the material of the present invention, and improve the tear resistance, bending resistance, flexibility, etc. of the material. Based on the dynamic property, when the microscopic damage in the material occurs, the self-repairing can be performed, the expansion of the microscopic damage is avoided, the integral damage of the material is caused, the service life of the material is prolonged, and the like. Shape memory, including the realization of secondary and multiple reshaping by the dynamic key/action in the shape memory, so as to obtain a secondary or subsequent temporary shape, and facilitate the obtainment of other shapes after one-time molding; the reshaped structure may then be restored to the original shape by appropriate means. The adaptability of the material in the use process is facilitated, for example, the appearance requirement of different people or articles is met, and the like. Wherein, the dynamic dilatancy is given by dynamic covalent bond/non-covalent effect, so that the dilatancy function which is cooperated and/or orthorhombic with the vitrification dilatancy can be obtained.

In the present invention, the hybrid dynamic polymer may further optionally contain entangled dilatant based on entangled dilatant polymer components, dispersed dilatant based on dispersed dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure, further enriching dilatant, and cooperativity and/or orthogonality thereof. For example, the characteristics of low sensitivity of dynamic dilatant to temperature, high dynamic transition speed and the like compared with vitrification dilatant can widen the dilatant temperature range of the polymer, and avoid the problems of rapid decrease of dilatant at low temperature and lack of flexibility of the material after hardening and embrittlement at low temperature; far more effective than the use of the vitreous dilatancy alone, and is difficult to achieve by adjusting the glass transition temperature of the vitreous dilatancy, the effect achieved is even unexpected. The air dilatancy can control the intensity of dilatancy by means of the cell structure of the dilatancy foam, and the dilatancy foam can obtain certain dilatancy characteristics under the impact of energy by the design of the special open cell structure, so that the energy absorption and protection performances of the foam are improved. The air dilatancy has the characteristic of insensitivity to temperature, is convenient for keep relatively stable dilatancy performance in a wider temperature range, and the shrinkage rate of the foam after cooling can be reduced by the partially open cell structure, so that the shape stability of the dilatancy foam is improved. The reasonable combination of multiple dilatant forming factors can obtain richer dilatant performance and other comprehensive performances, such as dilatant polymer materials with multiple dilatant performance, good low-temperature dilatant performance and good mechanical performance and structural support performance at high temperature. The solid microparticles and the dispersion liquid required for dispersibility and dilatancy have rich structures and properties, and by using the dispersion liquid of the solid microparticles in a proper combination, more diversified dilatancy properties can be obtained. In addition, because the dispersion liquid of the inorganic particles has the characteristic of better puncture resistance, the better comprehensive performance, such as better energy absorption and protection performance and spike and fracture prevention functions, can be conveniently obtained while the dilatant performance is obtained. These synergistic and orthogonal dilatancy properties impart unprecedented new properties to the materials of the present invention.

(2) In the present inventionWhen the dynamic unit in the dilatant hybrid dynamic polymer is only a supermolecule, the dynamic unit can be only a non-hydrogen bond supermolecule, and excellent anti-damage capability, molecular-level, micro-scale self-repairing property and rich functionalities such as luminescence, fluorescence, adsorption and the like can be provided through the diversity and the functionality of the non-hydrogen bond supermolecule. When the dynamic unit in the dilatant hybrid dynamic polymer is only hydrogen bond, the invention controls the performance of the polymer by controlling the number of teeth and the structure of the hydrogen bond, so as to achieve unexpected effect, for example, when the polymer is only bidentate or less, the hydrogen bond group with the number of teeth of the bidentate or less is selected from at least one of the following structural components:

these hydrogen bonding effects can reduce the occurrence of phase separation and/or crystallization, providing better dynamics; for example, when the hydrogen bonding action of the number of teeth of three teeth or more is introduced, higher dynamic bonding strength can be provided, mechanical properties such as mechanical strength and modulus of the dilatant polymer material are improved, and a shape memory function is realized.

(3) In the invention, two or more dynamic units, especially dynamic units with different stimulus responsivity/dynamic reversible conditions, are introduced into the dilatant hybrid dynamic polymer, so that the dynamic performance with orthogonality and multiple stimulus responsivity can be obtained, and the shape memory function can be obtained. In a preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form dynamic crosslinking, wherein one dynamic unit has light responsiveness, the other dynamic unit does not have light responsiveness, the dynamic reversible transformation of the former dynamic unit is induced by illumination, and the decrosslinking is realized, namely, temporary shaping effect is obtained, and the latter dynamic crosslinking can play a permanent shaping effect due to the fact that the dynamic crosslinking does not have light responsiveness, so that the shape memory performance of the dilatant polymer material is provided together. In another preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form a dynamic crosslinking effect, wherein the two dynamic units have photo-responsivity, but the photo-responsivity wavelength ranges of the two dynamic units are different, and the temporary shaping effect is obtained by regulating and controlling the irradiation wavelength to induce the de-crosslinking of part of the dynamic crosslinking effect, while the other dynamic crosslinking effect can play the role of permanent shaping and jointly provide the shape memory property of the dilatant polymer material because the other dynamic crosslinking effect can not generate dynamic reversible transformation under the irradiation of the wavelength. In another preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form a dynamic crosslinking effect, wherein the two dynamic units have temperature responsiveness, but the response temperatures of the two dynamic units are different, and the temporary shaping effect is obtained by regulating and controlling the temperature to induce the decrosslinking of part of the dynamic crosslinking effect, while the other dynamic crosslinking effect can play a role of permanent shaping because the dynamic crosslinking effect cannot be dynamically and reversibly converted at the temperature, so that the shape memory performance of the dilatant polymer material is provided together.

(4) In the invention, the dilatant hybrid dynamic polymer can contain common covalent crosslinking, dynamic covalent crosslinking and/or non-covalent crosslinking, and can obtain multi-level and gradient crosslinking by designing and adjusting the intensity of the dynamic crosslinking, thereby obtaining multi-level and/or gradient strength, dilatant, shape memory, toughness, self-repairing property and the like of the material. For example, when subjected to an external force, the weaker hydrogen bond breaks first (reversible) and then the dynamic covalent bond breaks. For example, through structural design, one side of the film material is crosslinked by metal ligand, and the other side is crosslinked by photodimerization to obtain dynamic covalent bond, and the two sides of the film are different in performance due to different crosslinking degree and bond/action strength, and the softer side is used for being close to a human body or an object, so that the comfort is improved; the stronger side is used for impact resistance. These are clearly tremendous innovations of the present invention.

(5) In the present invention, the network structure of the dilatant hybrid dynamic polymer is rich, and the dilatant hybrid dynamic polymer may contain only one crosslinked network (single network structure) or may contain at least two crosslinked networks (multi-network structure). The mechanical property, the dilatant property, the dynamic property and other using properties of the polymer can be regulated and controlled by reasonably designing the dilatant hybrid dynamic polymer cross-linked network structure. When the polymer contains only one crosslinked network, the structure is relatively simple and easy to prepare. In addition, based on the characteristics of a single network structure, the polymer structure can be conveniently regulated and controlled, and the polymer with single controllable glass transition temperature dilatant is also easy to obtain, so that the temperature controllability of the polymer dilatant process is improved (namely, the dilatant process can be realized in a narrower temperature range). When the polymer contains two or more than two cross-linked networks, the networks can be mutually inserted or partially mutually inserted or mutually blended and combined together, so that the mechanical strength and modulus of the dilatant material can be greatly improved, and the dilatant polymer gel or dilatant polymer foam has unique advantages in preparing high-strength dilatant polymer gel or dilatant polymer foam. The reasonable design of the multi-network structure can fully exert the functions of different polymer matrixes and different dynamic crosslinking, and the hybridization/combination/mixing of various dilatant structural factors and component factors, so that the dilatant hybrid dynamic polymer with multiple dilatant can be conveniently obtained, and the requirements of different application scenes on dilatant performance can be better met. In addition, through reasonable design of the multi-network structure, such as design and combination of proper dynamic units, the polymer is provided with shape memory performance together with common covalent crosslinking, and the existence of dynamic crosslinking is also helpful to realize super toughness, further widens the application field of the dilatant material, and the invention and the novelty are also embodied.

(6) In the invention, the crosslinked network of the dilatant hybrid dynamic polymer can be further dispersed or blended with a non-crosslinked structure, especially a non-crosslinked dilatant polymer containing a strong dynamic covalent bond and/or a strong dynamic non-covalent effect, which can impart additional dynamic dilatant to the polymer, is convenient for viscous flow through a chain segment thereof, and further improves energy absorption performance.

(7) In the present invention, the dilatant hybrid dynamic polymer is in various forms including but not limited to elastomers, gels, foams. Various forms of dilatant polymer materials have various structural characteristics and performance characteristics and can be reasonably designed and prepared according to practical application occasions.

(8) In the invention, the energy absorption method adopts the dilatant hybrid dynamic polymer as the energy absorption material for energy absorption application, and compared with the traditional polymer energy absorption material and the energy absorption method thereof, the energy absorption mechanism of the energy absorption method is very rich, besides the traditional energy absorption mechanism, the energy absorption method also comprises the steps of carrying out energy absorption through the dilatant of the polymer, carrying out energy absorption through the dynamic reversible transformation process of the dynamic covalent bond and the non-covalent effect contained in the polymer, and the like as a sacrificial bond, so that the energy absorption method can provide excellent energy absorption performance for the polymer energy absorption material and carry out effective energy absorption and impact resistance protection, thereby solving the problems of single energy absorption mechanism, poor energy absorption effect and the like of the traditional energy absorption material, and embodying the novelty and creativity of the invention. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

These and other features and advantages of the present invention will become apparent with reference to the following description of the embodiments, examples, and appended claims.

Detailed Description

The present invention will be described in detail below.

The invention relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bond and non-covalent function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the dynamic covalent bond and the non-covalent effect above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bond and non-covalent function.

The term "polymerization" reaction/action used in the present invention, unless otherwise specified, refers to a process in which a lower molecular weight reactant forms a product having a higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, or the like, that is, a chain growth process/action other than crosslinking. The reactant may be a monomer, oligomer, prepolymer or the like having a polymerization ability (i.e., capable of spontaneously polymerizing or capable of polymerizing under the action of an initiator or external energy). The product obtained by polymerizing one reactant is called a homopolymer. It is to be noted that "polymerization" as referred to in the present invention includes a linear growth process, a branching process, a cyclization process, and the like of reactant molecular chains other than the reactant molecular chain crosslinking process. In embodiments of the present invention, "polymerization" includes chain growth processes caused by the bonding of dynamic covalent bonds and ordinary covalent bonds, and non-covalent interactions/supramolecular interactions.

The term "crosslinking" reaction/action as used herein refers to the process of intermolecular and/or intramolecular bonding by dynamic covalent bonds and ordinary covalent bonds, as well as non-covalent interactions/supramolecular interactions, to form products having a three-dimensional infinite network. In the crosslinking process, the polymer chain is generally continuously grown in two-dimensional/three-dimensional directions, clusters are gradually formed (two-dimensional or three-dimensional), and then the polymer chain is developed into a three-dimensional infinite network crosslinking mode, which can be regarded as a special form of polymerization. During the crosslinking process, a three-dimensional infinite network is just reached. Thus, the degree of crosslinking, referred to as the gel point, is also referred to as the percolation threshold. A crosslinked product above (including, below) the gel point, having a three-dimensional infinite network structure, the crosslinked network forming a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only an open inter-chain linked structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can be formed as a whole across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention is a three-dimensional infinite network structure above the gel point, and the non-crosslinked (structure) refers to a structure such as a linear, cyclic, branched, and two-dimensional, three-dimensional cluster below the gel point, and a "combined" structure of the above structures.

In the invention, the linear structure refers to a polymer molecular chain which is in a regular or irregular long-chain linear shape and is generally formed by connecting a plurality of repeated units on a continuous length, and side groups in the polymer molecular chain are not generally in branched chains; for "linear structure", it is generally formed by polymerizing monomers not containing long chain side groups by polycondensation, polyaddition, ring opening, or the like.

In the present invention, the term "cyclic" means that the polymer molecular chain exists in the form of a cyclic chain, which includes a cyclic structure in the form of a single ring, multiple rings, bridged rings, nested rings, grommet rings, wheel rings, etc.; as for the "cyclic structure", it may be formed by intramolecular and/or intermolecular ring formation of a linear or branched polymer, or may be prepared by a method such as ring-expanding polymerization.

In the present invention, the term "branched" structure refers to a structure comprising side chains, branched chains, and branched chains on the polymer molecular chain, including but not limited to star-shaped, H-shaped, comb-shaped, branch-shaped, hyperbranched, and combinations thereof, and further combinations thereof with linear and cyclic structures, such as a linear chain end-linked cyclic structure, a cyclic structure combined with a comb-shaped structure, a branch-shaped chain end-linked cyclic chain, and the like; for "structures such as side chains, branches and bifurcation chains of a 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 molecule chain. As for the "branched structure", various methods for its preparation are generally known to those skilled in the art and can be formed, for example, by polycondensation of monomers containing long-chain side groups, or by chain transfer reactions of free radicals during the polyaddition, or by extension of branched structures on the linear molecular chain by irradiation and chemical reactions. The branched structure may be further subjected to intramolecular and/or intermolecular reactions (crosslinking) to produce clusters and crosslinked structures.

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 reactions of polymer chains.

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

In the invention, the combined form structure refers to a polymer structure containing two or more than two of structures such as two-dimensional and three-dimensional clusters below a linear, annular, branched and gel point, for example, a ring chain is used as a side chain of a comb-shaped chain, the ring chain is provided with the side chain to form a ring-shaped comb-shaped chain, the ring chain and the straight chain form a tadpole-shaped chain and a dumbbell-shaped chain, and the combined structure of the ring chain, the branched chain, the cluster and other topological structures is also included.

In the present invention, "skeleton" refers to the structure in the chain length direction of a polymer chain. Unless otherwise specified, it refers to the chain with the greatest number of links. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and distributed beside the main chain; wherein, the "branched chain"/"furcation chain" can be a side chain or other chain structure which is furcated from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and distributed beside the chain. Wherein, the term "end group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. The pendant groups, unless otherwise specified, refer specifically to groups of molecular weight not exceeding 1000Da attached to the side of the polymer chain backbone and to subunits therein. When the molecular weight of the side chain, the bifurcated chain, is not more than 1000Da, the group itself and the groups thereon are considered pendant groups. For simplicity, when the molecular weight of the side chain, the bifurcated chain, exceeds 1000Da, the term "side chain" is used generically unless otherwise specified. The "side chains", "side groups" described above may have a multi-stage structure, i.e., the side chains/side groups may continue to bear side chains/side groups, and the side chains/side groups of the side chains/side groups may continue to bear side chains/side groups. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer segment can be regarded as a side chain, and the rest can be regarded as a main chain.

For simplicity of explanation, 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 conjunction "and/or" previously described options, or from the conjunction "and/or" subsequently described options, or from the conjunction "and/or" previously and subsequently described options.

In addition, in the terms "group", "series", "sub-series", "class", "subclass" and "species" used to describe different structures in the present invention, the group is wider than the series, the series is wider than the sub-series, the sub-series is wider than the class, the class is wider than the subclass, and the sub-class is wider than the species, i.e. one group may have many series, one series may have many sub-series, one sub-series may have many classes, one class may have many sub-classes, and one sub-class may have many kinds.

In the present invention, even though the dynamic covalent bond or non-covalent motif has the same motif structure, it may cause a difference in properties thereof due to a difference in a linker, a substituent, an isomer, a complex structure, etc. In the present invention, unless otherwise specified, dynamic covalent bonds or non-covalent motifs having the same motif structure are generally regarded as different structures due to different structures such as linker, substituent, isomer, etc. In the present invention, when the polymer contains at least two dynamic covalent bond or non-covalent motifs, the at least two dynamic covalent bond or non-covalent motifs may be at least two different kinds of dynamic covalent bond or non-covalent motifs, or at least two different subclasses of dynamic covalent bond or non-covalent motifs, or at least two different families of dynamic covalent bond or non-covalent motifs, or at least two different groups of dynamic covalent bond or non-covalent motifs. The invention can reasonably design, select, regulate and combine dynamic covalent bond or non-covalent primitive according to the requirement to obtain the best performance, which is also an advantage of the invention.

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

In the present invention, the term "ordinary covalent bond" refers to a covalent bond other than a dynamic covalent bond in the conventional sense, which is an interaction formed between atoms through a common electron pair, and is difficult to break at a normal temperature (generally not higher than 100 ℃) and in a normal time (generally less than 1 day), and includes, but is not limited to, a normal carbon-boron bond, a carbon-carbon bond, a carbon-oxygen bond, a carbon-hydrogen bond, a carbon-nitrogen bond, a carbon-sulfur bond, a nitrogen-hydrogen bond, a nitrogen-oxygen bond, an hydrogen-oxygen bond, a nitrogen-nitrogen bond, and the like.

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 used herein unless otherwise specified, and may be defined as either the presence of chemical structural linkages/linkages or the physical mixing of specific means.

In the present invention, the dilatant hybrid dynamic polymer may be an unfoamed solid (including gel) or a foamed foam.

In the present invention, the dilatancy may also be referred to as shear thickening, which refers to a property in which the viscosity and/or strength and/or hardness of the polymer (composition)/dispersion composition increases with increasing rate of action of force under shear or other mechanical external forces.

In the present invention, the dilatant, in addition to the vitrified dilatant, optionally includes, but is not limited to, dynamic dilatant, tangled dilatant, dispersive dilatant, and aerodynamic dilatant. Wherein "vitrification dilatancy" is caused by the glass transition temperature of segments in the structure of the polymer itself; under the action of shearing force near the glass transition temperature, the polymer chain or chain segment cannot move in time along with the shearing rate so as to generate reversible freezing similar to the glass transition; or it can be seen that the shear rate causes a change in the glass transition temperature of the polymer chain or segment near the glass transition temperature under the action of shear forces near the glass transition temperature. Wherein "dynamic dilatancy" is caused by the introduction of strong dynamic non-covalent interactions and/or dynamic covalent bonds in the structure of the polymer itself, by which the polymer achieves the dilatancy process. The dynamic dilatancy also includes dilatancy based on dynamic covalent/non-covalent interactions between inorganic/organic particles and between polymers/small molecules etc. Wherein "entanglement dilatant" is achieved by utilizing molecular chain entanglement to cause the inability of the polymer chains to move in time when sheared. Wherein "dispersive dilatant" is a dilatant process achieved by the dispersion of solid microparticles in a dispersion medium, by the cluster effect/flowability of the dispersion. Wherein "pneumatic dilatancy" is achieved by regulating the cell structure of the foam, which is predominantly closed cell structure, but which also contains small-sized open cells, so that when the foam is compressed or backflushed, the gas slowly escapes or enters and thus exhibits dilatancy characteristics. In the embodiment of the present invention, the other dilatant component is not limited thereto. In embodiments of the present invention, the method of achieving dilatancy may also be a combination of two or more different ways including vitrification dilatancy including, but not limited to, a physically mixed form, a chemically hybridized form, both physically mixed and chemically hybridized forms.

In the present invention, the dilatant hybrid dynamic polymer contains at least vitrified dilatant, which means that the dilatant hybrid dynamic polymer may contain vitrified dilatant alone or may contain a combination of two or more different ways including vitrified dilatant, i.e. the dilatant hybrid dynamic polymer of the present invention contains vitrified dilatant and optionally at least one dilatant selected from dynamic dilatant, entanglement dilatant, dispersive dilatant and pneumatic dilatant. More specifically, the dilatant hybrid dynamic polymer optionally contains dynamic dilatant based on the contained vitrified dilatant polymer component, entanglement dilatant based on the dynamic dilatant polymer component, dispersive dilatant based on the dispersive dilatant composition and aerodynamic dilatant based on the aerodynamic dilatant structure in addition to vitrified dilatant based on the contained vitrified dilatant polymer component, further enriching dilatant, and cooperativity and/or orthogonality thereof.

In embodiments of the present invention, when two or more dilatant including vitrification dilatant are included in the dilatant hybrid dynamic polymer, it includes, but is not limited to, the method comprises the steps of physical mixing of vitrified dilatant and dynamic dilatant, physical mixing of vitrified dilatant and entanglement dilatant, physical mixing of vitrified dilatant and dispersive dilatant, physical mixing of vitrified dilatant and dynamic dilatant and entanglement dilatant, physical mixing of vitrified dilatant and dynamic dilatant and pneumatic dilatant, physical mixing of vitrified dilatant and dispersive dilatant and pneumatic dilatant, chemical hybridization forms of vitrified dilatant and dynamic dilatant on polymer chains, and chemical hybridization forms of vitrified dilatant and dynamic dilatant on polymer chains.

Wherein the physical mixing forms are vitrified dilatant polymer components, dynamic dilatant polymer components, entangled dilatant polymer components, dispersive dilatant compositions, aerodynamic dilatant structures which are mixed together in a physical blending form to realize dilatant of the prepared dilatant polymer, wherein the dilatant (polymer) components, compositions and structures are independent from each other in the polymer system; wherein the chemical hybrid forms are dilatant polymer components in different modes, including vitrified dilatant polymer components, dynamic dilatant polymer components and entanglement dilatant polymer components, are introduced into the same polymer chain or the same polymer network and are connected with each other in a chemical mode (including common covalent bond, weak dynamic covalent bond, weak dynamic non-covalent bond, strong dynamic covalent bond and strong dynamic non-covalent bond).

In the invention, the vitrification dilatant has higher sensitivity to temperature, shows better temperature responsiveness and reliability, and is greatly influenced by temperature. The dynamic dilatant has the characteristics of lower sensitivity to temperature than vitrification dilatant, high dynamic transformation speed and the like, can widen the dilatant temperature range of the polymer, and avoids the problem that the dilatant is rapidly reduced at low temperature and the problem that the material is hardened and becomes brittle and lacks flexibility at low temperature; far more effective than the use of the vitreous dilatancy alone, and is difficult to achieve by adjusting the glass transition temperature of the vitreous dilatancy, the effect achieved is even unexpected. The air dilatancy can control the intensity of dilatancy by means of the cell structure of the dilatancy foam, and the dilatancy foam can obtain certain dilatancy characteristics under the impact of energy by the design of the special open cell structure, so that the energy absorption and protection performances of the foam are improved. The air dilatancy has the characteristic of insensitivity to temperature, is convenient for keep relatively stable dilatancy performance in a wider temperature range, and the shrinkage rate of the foam after cooling can be reduced by the partially open cell structure, so that the shape stability of the dilatancy foam is improved. The reasonable combination of multiple dilatant forming factors can obtain richer dilatant performance and other comprehensive performances, such as dilatant polymer materials with multiple dilatant performance, good low-temperature dilatant performance and good mechanical performance and structural support performance at high temperature. The solid microparticles and the dispersion liquid required for dispersibility and dilatancy have rich structures and properties, and by using the dispersion liquid of the solid microparticles in a proper combination, more diversified dilatancy properties can be obtained. In addition, because the dispersion liquid of the inorganic particles has the characteristic of better puncture resistance, the better comprehensive performance, such as better energy absorption and protection performance and spike and fracture prevention functions, can be conveniently obtained while the dilatant performance is obtained. The combined use of two or more dilatants, including vitrified dilatant, has a richer performance profile than a single dilatant alone. For example, the combination of vitrified dilatant with dynamic dilatant, which is less sensitive to temperature, can lead to a broader dilatant temperature range of dilatant materials, avoiding the problem of a sharp decrease in dilatant at low temperatures; the physical mixing of vitrification dilatant and dispersion dilatant can lead the dilatant material to have higher sensitivity to temperature, show better temperature response and reliability, introduce dispersion dilatant composition, also can endow the material with the functions of spike prevention and fracture prevention, and enhance the practicability of the material; the physical combination of vitrification dilatant and pneumatic dilatant is convenient for keeping relatively stable dilatant performance in a wider temperature range, and is also beneficial to the molding stability of dilatant polymer foam and avoids the influence of shrinkage of the foam on the dimensional stability of the material; the physical mixing of vitrification dilatant, dynamic dilatant and dispersive dilatant can widen the dilatant temperature range of the dilatant material, wherein the sensitivity of the dynamic dilatant is lower, the problem of rapid decrease of dilatant at low temperature can be avoided, dispersive dilatant composition is introduced, the material can be endowed with spike and rupture preventing function, and the practicability of the material is enhanced; the physical mixing of vitrification dilatant and dynamic dilatant and the combination of pneumatic dilatant enable dilatant materials to absorb energy effectively in a relatively wide temperature range, particularly the dilatant materials can still keep energy absorbing performance well at low temperature, and the forming stability of foam can be improved due to the existence of a pneumatic dilatant structure; the physical mixing of vitrified dilatant and dispersive dilatant and the combination of pneumatic dilatant can lead the dilatant material not to drop sharply at low temperature, the existence of the pneumatic dilatant structure can also improve the forming stability of foam, and the introduction of dispersive dilatant composition can also endow the material with the functions of spike prevention and fracture prevention; the physical mixing of vitrified dilatant, dynamic dilatant and dispersive dilatant and the combination of pneumatic dilatant can give full play to the performance characteristics of various dilatants, obtain better dilatant performance, especially dilatant at low temperature, and meanwhile, the existence of the pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and also endow the material with spike and cutting prevention functions. These are clearly not available with conventional polymers, which represent the novelty and creativity of the present invention in achieving the polymer dilatancy approach.

In the present invention, the intrinsic type dilatant polymer means that the polymer itself has dilatancy, and can have dilatancy without the need of compounding, filling, dispersing, structural design other than molecules, and the like, with non-polymer components; the extrinsic dilatant polymer is required to be dilatant by preparing composite materials, compositions, etc. by compounding, filling, dispersing, structural design other than molecules, etc. In the present invention, the one intrinsic type dilatant polymer matrix may be one polymer, and may be composed of a plurality of intrinsic type dilatant polymers or a combination of an intrinsic type dilatant polymer and an extrinsic type dilatant polymer. Furthermore, a polymer composition is also considered to be an intrinsically dilatant polymer when non-covalent forces are formed between the components of the composition and dilatant is generated by the non-covalent forces or not by the non-covalent forces. The intrinsic dilatant polymer (composition) can show creep or slow rebound property under specific conditions, namely, the polymer can deform when being subjected to external force; after the external force is removed, the material cannot rebound; or not rebound/recover deformation immediately, but rebound/recover deformation slowly, with no or only a small residual deformation. In the present invention, the composite (composition) containing the intrinsic type dilatant polymer may still have dilatancy but may not exhibit creep or slow rebound characteristics, or have lower creep or slow rebound characteristics, or only have high rebound by blending and/or network interpenetration of the components such as the non-dilatant polymer and/or filler. The polymer composite (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 have high resilience. Polymers (compositions) containing pneumatic dilatancy are generally slow resilient.

In the present invention, the slow rebound time of the dilatant hybrid dynamic polymer (composition) having slow rebound at normal temperature and pressure is not particularly limited, but is preferably 0.5 seconds to 120 seconds, more preferably 1 second to 60 seconds, still more preferably 1 second to 10 seconds. The slow rebound time refers to the time required for basically recovering the sample after applying a collapse force to the sample to generate a prescribed deformation and keeping the prescribed time. When the polymer is in the form of an elastomer or gel, it is pressed into 40% of the initial thickness of the sample under pressure, held for 60 seconds, and the time required for the sample to recover to the deformation position of 3% of the initial thickness is measured and recorded as the slow rebound time; when the polymer form is foam, it is pressed into 75% of the original thickness of the test specimen under pressure, and held for 60 seconds, the time required for the sample to recover to the deformation position of 5% of the original thickness is measured and recorded as its slow rebound time.

In the present invention, the dilatant hybrid dynamic polymer, when in the form of an elastomer or gel, preferably has a 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%, and wherein the test method is ASTM D-2632"Rubber Property-Resiliency by Vertical Rebound" (ASTM D-2632, "rubber properties-vertical rebound"); when in the form of a foam, it preferably has a rebound of less than 50%, more preferably a rebound of 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, bonded andMolded Urethane Foams, test H, resilience (Ball Rebound) Test" (ASTM D-3574H, "Flexible cellular Material-Board, adhesive and molded polyurethane foam, test H, rebound (ball rebound) Test").

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

rebound r=h/H100%;

wherein h is rebound height in millimeters (mm);

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

In the present invention, the dilatant hybrid dynamic polymer has at least one or more glass transition temperatures and preferably has at least one glass transition temperature in the range of-40 ℃ to 60 ℃ in the soft segment and/or the inter-crosslinking point segment. In the present invention, having the glass transition temperature is one of the requirements for achieving the polymer of the present invention with a vitrification dilatant property, i.e. the vitrification dilatant property utilizes at least the glass transition of the polymer, in particular the glass transition of its soft segment structure. The glass transition temperature refers to the transition temperature of the polymer from a brittle glass to an elastic rubbery state, i.e., the temperature at which the glass transition occurs, and may be a temperature point or a temperature range (also referred to as a glass transition region). When the polymer temperature drops below its glass transition temperature, the molecular chains and segmental movements of the polymer are frozen, exhibiting brittleness; as the polymer temperature increases and exceeds its glass transition temperature, both the molecular chains and segments of the polymer are mobile, exhibiting high elasticity in the viscous or rubbery state; around the glass transition temperature, the polymer segments in the polymer are in a freeze-thaw state, the segments are mobile but the molecular chain motion is limited, exhibiting good viscoelasticity, and thus obtaining dilatant properties. When the glass transition temperature of the polymer is around room temperature, the polymer may exhibit room temperature vitrification dilatant properties; when its glass transition temperature is around other temperatures, vitrification dilatancy can be achieved in other temperature ranges.

In the present invention, the glass transition temperature (Tg) of the polymer can be measured by a person skilled in the art by a well-known test method. For example, the measurement can be performed at least by a method for measuring a glass transition temperature commonly used in the art, such as Differential Scanning Calorimetry (DSC), dynamic mechanical analysis/Dynamic Mechanical Analysis (DMA), dynamic mechanical thermal analysis/Dynamic Mechanical Thermal Analysis (DMTA), and the like.

In the present invention, the temperature range (temperature span) of any one of the glass transition temperatures of the dilatant hybrid dynamic polymer is not particularly limited but depends on the use temperature range thereof. When the glass transition temperature is only one and the range is wide or a plurality of the glass transition temperatures are wide, the polymer can realize the dilatant process in a wide temperature range, and thus a wide dilatant use temperature range is obtained, and the problem of hardening of the polymer caused by temperature reduction (i.e., low-temperature hardening problem) can be avoided to some extent; when the glass transition temperature range is narrow, the dilatant temperature range of the polymer is narrow, and the temperature controllability and the temperature dependence of the dilatant process are better.

In the present invention, the glassy dilatant may be obtained by incorporating in the polymer a glassy dilatant polymer composition, which refers to a polymer segment (also including oligomer segments, hereinafter also referred to as such) having at least one glass transition temperature, preferably at least one polymer segment having a glass transition temperature in the range of-40 ℃ to 60 ℃, which may be a soft segment and/or a cross-linking point segment of the dilatant polymer. The vitreous dilatant polymer component described in the present invention may be chemically linked to the linking segments of the dilatant polymer cross-linked network polymer chains as cross-linked network or may be dispersed in the cross-linked network in a physically blended form, preferably introduced into the cross-linked network polymer chains in a chemically linked form, to obtain a dilatant process of greater reliability and stability.

In a preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has only one glass transition temperature, the glass transition temperature being in the range of-40 ℃ to 60 ℃; preferably at-10 to 40 ℃. In this embodiment, the soft segment and/or inter-crosslinking point segment of the polymer has only one glass transition temperature, and when it has a narrower glass transition temperature span, the glassy dilatant/slow rebound process is more temperature dependent and responsive, i.e. is capable of exhibiting viscoelasticity over a narrower temperature range; when it has a wider glass transition temperature span, its dilatancy/slow rebound process is less temperature dependent and can accommodate a wider application temperature.

In another preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has at least two glass transition temperatures, one of which is between-60 ℃ and 0 ℃, preferably between-40 ℃ and 0 ℃; the other glass transition temperature is between 0 ℃ and 80 ℃, preferably between 0 ℃ and 40 ℃; preferably, the two glass transition temperatures have an overlap. In the embodiment, the combination of different soft segment glass transition temperatures enables the polymer to have a wider vitrification dilatancy/slow rebound temperature range, so that the polymer material can have a wide vitrification dilatancy/slow rebound use temperature. In embodiments of the present invention, the glassy dilatant polymer may be prepared at least by the use of a mixture of soft segments and/or inter-crosslinking point segments of different compositions and/or soft segments and/or inter-crosslinking point segments of different molecular weights and/or different soft segments and/or inter-crosslinking point segments to achieve a plurality of glass transition processes that are broad and continuous to widen the temperature range of use, e.g., winter polar low temperatures to summer desert high temperatures.

In another preferred embodiment of the present invention, the soft segment and/or the inter-crosslinking point segment of the dilatant hybrid dynamic polymer has at least two glass transition temperatures, one of which is between-40 ℃ and 60 ℃, preferably between-10 ℃ and 40 ℃; the other glass transition temperature is between-100 ℃ and-40 ℃; preferably at-80℃to-50 ℃. In this embodiment, the dilatant polymer has a relatively low glass transition temperature through the combination of different soft segment glass transition temperatures, so that the dilatant material has excellent low-temperature dilatant property, and the problems of hardening, loss of dilatant property and the like of the dilatant material at low temperature can be effectively avoided, so that the dilatant material still can effectively absorb energy at low temperature, and the dilatant material is better suitable for application scenes of low temperature even very low use temperature.

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 polymer soft segment and/or the chain segment between crosslinking points, so that the polymer is close to the using temperature of the dilatant material, and the maximum vitrification dilatant/slow rebound resilience is obtained.

In the embodiment of the present invention, the chemical composition of the polymer soft segment and/or the inter-crosslinking point segment having the vitrification dilatancy is not particularly limited, but is selected from, but not limited to, polymer segments whose main chain is a carbon chain structure, a carbon hybrid chain structure, a carbon element chain structure, an element hybrid chain structure, a carbon hybrid element chain structure, preferably a carbon chain structure, a carbon hybrid chain structure, an element hybrid chain structure, and a carbon hybrid element chain structure, because raw materials thereof are easily available and the preparation technology is mature, depending on the use temperature range thereof. By way of example, the polymer soft segments and/or inter-crosslinking point segments may be segments based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modifications, derivatives, and the like of acrylic acid ester 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; homopolymers, copolymers, modified products, derivatives, and the like of acrylic polymers, unsaturated olefin polymers, polyether polymers, epoxy polymers, polythioether polymers, and polysilicone polymers are preferable. By way of example, the polymer soft segments and/or inter-crosslinking point segments may be segments based on the following polymers, but the invention is not limited thereto: polyvinyl methyl ether (Tg of-13 ℃), polyvinyl ethyl ether (Tg of-42 ℃), polyvinyl propyl ether (Tg of-48 ℃), polyvinyl isopropyl ether (Tg of-14 ℃), polyvinyl butyl ether (Tg of-53 ℃), polyvinyl isobutyl ether (Tg of-13 ℃), polymethyl methacrylate (Tg of 10 ℃), polyethyl acrylate (Tg of-23 ℃), n-butyl acrylate (Tg of-54 ℃), isobutyl polyacrylate (Tg of-4 ℃), t-butyl acrylate (Tg of 43 ℃), polyacrylic acid-2-ethylhexyl ester (Tg of-70 ℃), n-octyl acrylate (Tg of-15 ℃), polyhydroxyethyl acrylate (Tg of-15 ℃), polyhydroxypropyl acrylate (Tg of-7 ℃), polyisopropyl methacrylate (Tg of 48 ℃), polybutyl methacrylate (Tg of 20 ℃), polyisobutyl methacrylate (Tg of 53 ℃), polyhexamethyl methacrylate (Tg of-5 ℃), polyhydroxyethyl methacrylate (Tg of 55 ℃), polyacrylic acid of 2-methoxyethyl acrylate (Tg of-34), polyethylene (methoxy acrylate of-2-34), polyethylene (methoxy acrylate of-20 ℃) Polymethyl (tetrahydrofuran-2-yl) acrylate (Tg of-13 ℃), benzyl polyacrylate (Tg of 4 ℃), 2-phenoxyethyl polyacrylate (Tg of 6 ℃), ethyl poly (2- (phenylthio) acrylate (Tg of 12 ℃), poly (2-phenoxyethoxy) ethyl acrylate (Tg of 12 ℃), polymethyl methacrylate (Tg of 105 ℃), polyethyl methacrylate (Tg of 65 ℃), hydroxypropyl polymethacrylate (Tg of 73 ℃), cyclohexyl methacrylate (Tg of 83 ℃), polyisobornyl methacrylate (Tg of 110 ℃), phenyl polyacrylate (Tg of 63 ℃), polyvinyl acetate (Tg of 32 ℃), polyvinyl chloride (Tg of 78 ℃), polyacrylic acid (Tg of 105 ℃), polymethacrylic acid (Tg of 185 ℃), polyacrylonitrile (Tg of 96 ℃), polyacrylamide (Tg of 165 ℃), polystyrene (Tg of 100 ℃), toluylene (Tg of 173 ℃), polycistronic acid (Tg of 131), polyethylene-propylene, polypropylene oxide, 1-isoprene, polybutylene, 1-4-epoxypropane, polybutadiene, 4-norbornene, 4-styrene-butadiene, 4-styrene, 4-butadiene, 4-styrene, norbornene, and the like copolymer) Ethylene oxide-propylene oxide copolymers (e.g., polyethylene oxide-polypropylene oxide copolymers), homopolymers, copolymers, modifications, derivatives, and the like of polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, hydrogen-containing polysiloxanes, and the like. 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. Wherein, the homopolymers, copolymers, modifications and derivatives of the unsaturated olefin polymers, polyether polymers, organosilicon polymers and the like have lower glass transition temperatures. Wherein, the glass transition temperature of the organosilicon polymers such as polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, homopolymers, copolymers, modified substances, derivatives and the like of hydrogen-containing polysiloxane is lower, and is usually between minus 130 ℃ and minus 60 ℃; unsaturated olefin polymers such as polyisobutylene, polybutadiene, polychloroprene, poly-cis-1, 4-isoprene, poly-trans-1, 4-isoprene, styrene-butadiene copolymers, and butadiene-acrylonitrile copolymers have relatively low glass transition temperatures, typically in the range of-110℃to-10 ℃.

In an embodiment of the present invention, the polymer soft segment and/or the cross-linking point segment with vitrification dilatancy may be a macromolecular segment with a molecular weight greater than 1000Da, or may be an oligomer or a small molecule connecting segment with a molecular weight lower than 1000 Da.

In an embodiment of the present invention, the topology of the polymer soft segment and/or inter-crosslinking point segment with vitrification dilatancy includes, but is not limited to, straight chain structures, branched structures (including but not limited to star, H-type, dendritic, comb, hyperbranched), cyclic structures (including but not limited to single ring, multiple ring, bridge ring, grommet, wheel ring), two-dimensional/three-dimensional cluster structures, and combinations of two or more thereof; among them, a linear structure and a branched structure are preferable. The linear structure has a simple structure, is easy to regulate and control the synthesis and control structure, and is easy to obtain a single glass transition temperature or a glass transition zone with a narrow temperature range, so that the dependence and the responsiveness of vitrification dilatancy/slow rebound performance on the environmental temperature are improved. And the branched structure has the structures of side chains, branched chains and the like, so that the glass transition temperature of the polymer is easy to reduce and regulate, and the low-temperature dilatancy/slow rebound performance is improved.

In the invention, the vitrification dilatant caused by the glass transition temperature of the polymer has the characteristic of strong adjustability of the working temperature range, and is convenient for obtaining dilatant materials with specific working temperature ranges.

In the embodiment of the invention, the glass transition temperature of the dilatant polymer is reasonably regulated, so that the dilatant polymer material has stable vitrification dilatant in a single temperature (a narrow temperature range), a plurality of temperatures or a wide temperature range, and the dilatant polymer material can better adapt to the requirements of application scenes at different temperatures on the dilatant performance of the material. For example, a dilatant polymer material having a single glass transition temperature and a small glass transition temperature span has a high sensitivity to temperature and shows a good temperature responsiveness and reliability; as another example, a dilatant polymer material having multiple glass transition temperatures, which is capable of having dilatancy at multiple temperature points/temperature intervals, can better accommodate application scenarios that require use at multiple different temperatures at the same time; as another example, the dilatant polymer material with a wider glass transition temperature span can play an effective energy absorbing role from extremely low temperature in winter to high temperature in desert in summer. Particularly, when the dilatant polymer material with dilatant property near room temperature can be used as protective headrests, seat filling materials, mattresses, shoe materials, sports protective mats, protective auto parts and other products, the dilatant polymer material can better relieve the pressure and fatigue of various parts of the body and provide better energy-absorbing protective effects, and is also helpful for obtaining room temperature slow rebound resilience, so that the problem of secondary injury of protective personnel and protective articles caused by the high-speed rebound process after the impact of the traditional energy-absorbing material is avoided; the dilatant polymer material with dilatant at room temperature and low temperature can effectively avoid the problems of material hardening and dilatant loss at low temperature, so that the dilatant polymer material can still effectively absorb energy at low temperature, and is better suitable for application scenes of low temperature even very low use temperature; meanwhile, the dilatant polymer material with glass transition temperature near room temperature and at middle and high temperature can not only keep stable dilatant at room temperature, but also avoid the problems of reduced material support and rapid decline or even complete loss of dilatant when the temperature is increased, and improve the practicability and reliability of the dilatant polymer material; the dilatant polymer materials with glass transition temperatures at low temperature, room temperature and medium and high temperature can realize dilatant in a wider temperature range, and can be better suitable for harsher application scenes of the dilatant polymer materials.

In an embodiment of the present invention, the glassy dilatant polymer component contained in the dilatant hybrid dynamic polymer may be dispersed in a non-glassy dilatant polymer cross-linked network of dilatant polymer in a non-cross-linked form providing glassy dilatant; the vitrification dilatant polymer component can be crosslinked by one or more structures of a common covalent bond, a weak dynamic non-covalent bond, a strong dynamic covalent bond and a strong dynamic non-covalent bond, and is introduced into a polymer to provide vitrification dilatant; the same or different non-crosslinked glassy dilatant polymer components may also be dispersed in a polymer crosslinked network having glassy dilatant properties to collectively provide glassy dilatant properties. The present invention also does not exclude non-crosslinked glassy dilatant polymer components as dilatant hybrid dynamic polymers according to the present invention.

In the present invention, a dynamic dilatant polymer composition refers to a polymer (including oligomer) comprising at least one strongly dynamic non-covalent and/or strongly dynamic covalent bond. This is achieved by suitable dynamic covalent/non-covalent interactions contained in the hybrid dynamic polymers of the invention.

In an embodiment of the present invention, the dynamic dilatant polymer component contained in the dilatant hybrid dynamic polymer may contain only the strong dynamic non-covalent effect, may contain only the strong dynamic covalent bond, and may also contain both the strong dynamic non-covalent effect and the strong dynamic covalent bond.

In embodiments of the present invention, typical strong dynamic non-covalent interactions include, but are not limited to: mono-dentate hydrogen bonding, di-dentate hydrogen bonding, mono-dentate metal-ligand bonding, di-dentate metal-ligand bonding, ionic-dipole bonding, host-guest bonding, metalphilic bonding, dipole-dipole bonding, halogen bonding, lewis acid base pairing, cation-pi bonding, anion-pi bonding, benzene-fluorobenzene bonding, pi-pi stacking, ionic hydrogen bonding, free radical cation dimerization; typical highly dynamic covalent bonds include, but are not limited to: boron-containing dynamic covalent bonds, dynamic covalent bonds of metal acid esters, and dynamic covalent bonds based on reversible free radicals. Among them, preferred is a monodentate hydrogen bonding action, a bidentate hydrogen bonding action, a monodentate metal-ligand action, an ion cluster action, an ion-dipole action, a host-guest action, a Lewis acid-base pair action, an ion hydrogen bonding action, an inorganic boric acid monoester bond, a saturated five-membered ring inorganic boric acid ester bond, an unsaturated five-membered ring inorganic boric acid ester bond, an organic boric acid monoester bond, a saturated five-membered ring organic boric acid ester bond, an unsaturated five-membered ring organic boric acid ester bond, a saturated six-membered ring organic boric acid ester bond, an unsaturated six-membered ring organic boric acid ester bond (especially a saturated five-membered ring organic boric acid ester bond/an unsaturated six-membered ring organic boric acid ester bond) to which aminomethyl phenyl groups are bonded, an inorganic boric acid silicone ester bond, an organic boric acid silicone ester bond, a dynamic silicon titanate ester bond, more preferably, the one-tooth hydrogen bonding, the two-tooth hydrogen bonding, the one-tooth metal-ligand bonding, the ion-dipole bonding, the host-guest bonding, the ion bonding, the inorganic boric acid monoester bond, the organic boric acid monoester bond, the saturated five-membered ring organic boric acid ester bond with aminomethyl phenyl group, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond, the unsaturated six-membered ring organic boric acid ester bond, the inorganic boric acid silicone ester bond, the organic boric acid silicone ester bond and the dynamic titanic acid silicone ester bond are high in dynamic property and good in regulation and control performance.

In an embodiment of the present invention, the dynamic exchange rate of the strong dynamic non-covalent interaction/dynamic covalent bond is preferably in the range of 100000 to 0.0001s ^-1 Depending on the different performance requirements and application, it may be preferable to use it for 1000-0.001s ^-1 Can be preferably in the range of 100 to 0.01s ^-1 It is also preferable to be 10 to 0.1s ^-1 . Different exchange rates in combination with different polymer structures, such as cross-linking degree, polymer chain topology, cross-linked network topology, glass transition temperature, composite structure, etc., can provide different force response rates and dilatancy, resulting in different viscous-elastic transitions or elastic enhancements, and thus different energy absorbing effects and rebound responses. The technical scheme of the invention can skillfully and effectively design and regulate dynamic dilatancy by designing and selecting proper dynamic units (namely dynamic covalent bond and non-covalent function) and polymer structures so as to meet the requirements of different performances in different occasions to the maximum extent. For example, a higher rate may meet higher cushioning requirements for an aged shoe, a lower rate may meet both cushioning and high rebound requirements for sprinting, jumping, etc., a lower rate may meet low creep requirements for shock absorption for precision instruments, etc.

In the invention, dynamic dilatancy caused by strong dynamic non-covalent action and/or dynamic covalent bond has the characteristics of rich regulation means, high dynamic transformation speed and the like. In the embodiment of the invention, by designing and selecting proper dynamic dilatant polymer components, various combined dilatant containing dynamic dilatant can be effectively designed and regulated, and excellent comprehensive dilatant can be obtained.

In the present invention, the chemical composition of the soft segment and/or the inter-crosslinking point segment of the polymer is not particularly limited, but is also selected from, but not limited to, polymer segments whose main chain is a carbon chain structure, a carbon hybrid chain structure, a carbon element chain structure, an element hybrid chain structure, a carbon hybrid element chain structure, preferably a carbon chain structure, a carbon hybrid chain structure, an element hybrid chain structure, and a carbon hybrid element chain structure, because of the availability of raw materials and the maturity of the preparation technology, depending on the temperature range of the polymer. In embodiments of the present invention, the soft segment and/or inter-crosslinking point segments of the dynamic dilatant polymer preferably have a low glass transition temperature, preferably no higher than 25 ℃, more preferably no higher than 0 ℃, more preferably no higher than-40 ℃, more preferably no higher than-100 ℃, in order to have a broad use temperature range, i.e. to be able to be used at low temperatures (e.g. in northern areas) and at high temperatures (e.g. in southern areas).

In an embodiment of the present invention, the dynamic dilatant polymer component contained in the dilatant hybrid dynamic polymer, which can be dispersed in a non-crosslinked form in a crosslinked network of polymers having vitrification dilatant properties, provides the dilatant polymer with dynamic dilatant properties; the dynamic dilatant polymer component can be crosslinked by the contained strong dynamic covalent bond and/or strong dynamic noncovalent action to form a polymer crosslinked network with dynamic dilatant property, so as to provide dynamic dilatant property, and the vitrified dilatant polymer component is crosslinked by the strong dynamic covalent bond and/or strong dynamic noncovalent action to provide dynamic dilatant property; the dynamic dilatant polymer component can be crosslinked by the contained strong dynamic covalent bond and/or strong dynamic non-covalent action to form a polymer crosslinked network with dynamic dilatant, and then the polymer crosslinked network with vitrification dilatant is combined together in a physical dispersion mode, an interpenetrating mode, a partially interpenetrating mode or the like to provide the dynamic dilatant. In the embodiment of the invention, a strong dynamic covalent bond and/or a strong dynamic non-covalent effect can be introduced into a polymer crosslinked network with vitrification dilatant to obtain a dynamic dilatant polymer component and provide dynamic dilatant. However, the invention is not limited thereto, i.e. as long as said dynamic dilatancy is achieved by inclusion of said dynamic covalent/non-covalent interactions, chemical hybridization and/or physical mixing of the aforementioned wave-forming dilatancy mechanisms; depending on the specific performance requirements and material structure, the various embodiments have their own advantages, which is also a flexibility and scalability of the present invention.

In the present invention, the entangled dilatant polymer component means a polymer component capable of achieving dilatancy by entanglement of polymer molecular chains such that the polymer chains cannot move in time when subjected to shear. In embodiments of the present invention, it is preferred that the molecular chains of the entangled dilatant polymer have a glass transition temperature of not higher than-20 ℃, more preferably not higher than-40 ℃, more preferably not higher than-60 ℃, more preferably not higher than-100 ℃. In an embodiment of the invention, the molecular weight of the entangled dilatant polymer needs to be high enough to obtain the entanglement effect under shear, preferably not lower than 100kDa, more preferably not lower than 1000kDa.

In an embodiment of the present invention, the entangled dilatant polymer component contained in the dilatant hybrid dynamic polymer, which can be dispersed in a non-crosslinked form in a crosslinked network of a polymer having vitrification dilatant properties, provides the dilatant polymer with entangled dilatant properties; the entangled dilatant polymer composition may also be covalently or non-covalently linked to the cross-linked network in the form of side chains, terminal chains, providing entangled dilatancy.

In the present invention, the dispersible dilatant composition contains at least 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%, still more preferably not less than 40%.

Wherein the solid microparticles comprise nanoparticles and microparticles; as examples, the former includes, but is not limited to, nano silica, nano alumina, nano montmorillonite, nano calcium carbonate, graphene, cellulose crystallites, nano polymethyl methacrylate 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, polymethyl methacrylate particles, polystyrene particles, starch particles, mica, silicon nitride, and the like. The solid microparticles can be in the shape of spheres, ellipsoids, discs, other regular and irregular polyhedrons, etc., and the surface of the solid microparticles can be smooth or rough, preferably spheres and ellipsoids; the surface of which is optionally also organically and/or inorganically modified.

Wherein, when the dispersion medium is selected from liquid, it includes but is not limited to organic matters, mineral oil, macromolecule matrix, etc., concretely, 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 mixture thereof; the dispersion medium, when selected from the group consisting of solids, 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 solid microparticles in the dispersion liquid are inorganic and the dispersion medium is organic, the dispersion liquid may further optionally contain a coupling agent and/or a surfactant, so that the solid microparticles may be more uniformly dispersed in the dispersion medium, such as silane coupling agents KH550, KH560, a1120, etc., and coupling agents such as titanates, aluminates, organochromates, phosphates, zirconates, stannates, etc.

In the present invention, the dispersible dilatant composition is preferably swollen or dispersed in a polymer network (including a polymer cross-linked network having a vitrifiable dilatant); or by coating, dipping, etc. in a self-supporting porous, hollow polymeric material (including vitrified dilatant polymers). Such polymeric materials include, but are not limited to, polymeric foams, fibrous 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 polymers on which the fibrous web is based include, but are not limited to, ultra-high molecular weight polyethylene, polypropylene, polyurethane, polyamide, polyaramid, polyester, polyarylate, polyurea, polyoxymethylene, polyimide, polyamide-hydrazide, polybenzimidazole, polyacrylonitrile, polyvinyl acetal, polyvinyl chloride, polyvinylidene chloride, silk, wool, cotton, hemp, cellulose esters, cellulose, other polymer alloys containing two or more polymers, and the like; the fibers of the fiber fabric can be homogeneous, or can be of a single-layer or multi-layer protective sleeve-core structure; the fiber fabric may be two-dimensional or three-dimensional, and may accommodate more dispersion/dispersion due to the higher porosity of the three-dimensional fiber fabric, providing better dispersion dilatancy.

In the invention, the solid microparticles and the dispersion liquid/dispersion needed for realizing the dispersibility dilatant have rich commercial sources, the dispersion process does not need to carry out complex chemical reaction, and the invention has the characteristic of high performance controllability. The dispersion of inorganic particles also has the characteristic of puncture resistance.

In the invention, when the form of the dilatant hybrid dynamic polymer is foam, the rebound time is increased and the dilatant is enhanced by controlling the open cell structure of the foam, generally when the open cell surface area ratio is reduced. In order to obtain a suitable dilatancy, the ratio of open area to cell surface area is preferably 3% to 20%, more preferably 5% to 15%, still more preferably 5% to 10%.

In the present invention, the cell structure with partial opening is considered as a gas-dynamic dilatant structure.

In the present invention, the cell structure of the polymer foam having pneumatic dilatancy can be obtained at least by adding an appropriate amount of a cell opening/pore forming agent. The cell opener/porogen, which may act to break cell walls as the polymer reacts to form a foam, thereby promoting the formation of an open cell structure. The types and the addition content of the pore-forming agent/porogen are not particularly limited, and can be reasonably regulated and controlled according to actual needs so as to obtain polymer foam with different open cell 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: an ethylene oxide homopolymer polyol having a molecular weight of greater than 5000Da and a hydroxyl functionality of not less than 5 or a random copolymer polyol of ethylene oxide and a small amount of propylene oxide, a propylene oxide homopolymer monol having a molecular weight of from 1000 to 8500Da and a hydroxyl functionality of 1.

In the invention, the pneumatic dilatant has the characteristic of insensitive temperature, is convenient for keeping relatively stable dilatant performance in a wider temperature range, and the partially open cell structure can reduce the shrinkage rate of the foam after cooling and improve the molding stability of the dilatant foam.

In the invention, the dilatant hybrid dynamic polymer is of a crosslinked structure, namely the dilatant hybrid dynamic polymer at least comprises a crosslinked network, the crosslinking degree of common covalent crosslinking in the crosslinked network is above a gel point, continuous structural stability and excellent mechanical property are provided for the polymer, plastic deformation of dilatant polymer materials is effectively avoided or reduced, continuous structural stability can be provided in the dynamic reversible transformation process of the contained dynamic covalent bonds and/or non-covalent effects, material disintegration is avoided, and the structural stability and use safety of the dilatant material can be greatly improved. Wherein, the cross-linked structure can be dispersed or blended with a non-cross-linked structure.

In the invention, the dilatant hybrid dynamic polymer can contain dynamic covalent crosslinking and/or non-covalent crosslinking besides common covalent crosslinking so as to obtain dynamic covalent and non-covalent dynamic properties and realize richer dynamic stimulus responsiveness. Based on the dynamic reversibility of the contained dynamic crosslinking, the molecular level and microcosmic self-repairing performance can be provided for the polymer, and the polymer can also be used as a sacrificial bond for absorbing energy, improving toughness and improving damage resistance. In particular, a weak dynamic cross-linking above the gel point is introduced into the polymer, which can also provide a shape memory function to the polymer together with a common covalent cross-linking; the high dynamic cross-linking is introduced into the polymer, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like. The dilatant hybrid dynamic polymer can only contain one dynamic covalent bond and one non-covalent function, can also contain a combination of multiple dynamic covalent bonds and one non-covalent function, can also contain a combination of one dynamic covalent bond and multiple non-covalent functions, can also contain a combination of multiple dynamic covalent bonds and multiple non-covalent functions, and the dynamic strength of the dynamic covalent bonds and the non-covalent functions can be reasonably selected and combined according to the use requirement so as to achieve optimal performance, and can meet the requirements of various different application scenes, so that the invention is creative and novel.

In the present invention, the dynamic units contained in the dilatant hybrid dynamic polymer (i.e., the dynamic covalent bonds and non-covalent interactions described in the present invention) can all cross-link to form dynamic cross-links (including dynamic covalent cross-links and non-covalent cross-links as well as hybrid dynamic cross-links); it is also possible to carry out only polymerization, grafting, functionalization, etc. without crosslinking; it is also possible that part of the dynamic units are crosslinked and part of the dynamic units are not crosslinked. In the embodiment of the invention, the dynamic units preferably play a role in crosslinking so as to improve the mechanical property, dilatant property, self-repairing property and comprehensive energy absorption property of the material. Without being particularly limited, any of the dynamic covalent bonds and noncovalent interactions contained in the crosslinked network described in the present invention exist in the polymer chain backbone of the crosslinked network, so that they participate in the formation of the crosslinked network and impart dynamic reversibility to the crosslinked structure thereof, better achieving synergistic dilatancy and achieving molecular and microscopic self-healing properties, shape memory properties, and improving the strength, toughness, fracture resistance, etc. of the material.

In the invention, the dilatant hybrid dynamic polymer can contain common covalent crosslinking, dynamic covalent crosslinking and/or non-covalent crosslinking, and can obtain multi-level and gradient crosslinking by designing and adjusting the intensity of the dynamic crosslinking, thereby obtaining multi-level and/or gradient strength, dilatant, shape memory, toughness, self-repairing property and the like of the material. For example, when subjected to an external force, the weaker hydrogen bond breaks first (reversible) and then the dynamic covalent bond breaks. For example, through structural design, one side of the film material is crosslinked by metal ligand, and the other side is crosslinked by photodimerization to obtain dynamic covalent bond, and the two sides of the film are different in performance due to different crosslinking degree and bond/action strength, and the softer side is used for being close to a human body or an object, so that the comfort is improved; the stronger side is used for impact resistance. These are clearly tremendous innovations of the present invention.

In the present invention, the term "ordinary covalent crosslinking" refers to a crosslinked structure formed only by ordinary covalent bonds. In the invention, the degree of crosslinking of the ordinary covalent crosslinks in the crosslinked network is above the gel point, which means that the crosslinked network still exists when only ordinary covalent bonds (neither dynamic covalent bonds nor non-covalent interactions nor dissociation) exist in the crosslinked network; the degree of crosslinking of the ordinary covalent crosslinks in the crosslinked network is below the gel point, which means that the crosslinked network cannot continue to be maintained when only ordinary covalent bonds (neither dynamic covalent bonds nor non-covalent interactions nor dissociation) are present in the crosslinked network. The crosslinked network formed by common covalent crosslinking is the common covalent crosslinked network.

In the invention, the dynamic covalent crosslinking refers to a crosslinking structure formed by the joint participation of a dynamic covalent bond and a common covalent bond, and the crosslinking degree of the common covalent crosslinking in a crosslinking network is below a gel point (the common covalent crosslinking does not exist in the crosslinking network), wherein the crosslinking formed by the dynamic covalent bond is a necessary condition for forming the crosslinking network; based on the reversible characteristic of the dynamic covalent crosslinking, the formed crosslinked network can carry out dissociation-bonding balance of the crosslinked network under proper conditions, and the dynamic reversibility is shown. The cross-linked network formed by dynamic covalent cross-linking is the dynamic covalent cross-linked network. It should be noted that when the dynamic covalent cross-linked network contains two or more dynamic covalent bonds and at least one dynamic covalent bond is a weak dynamic covalent bond, it is regarded as a weak dynamic covalent cross-linked network; a dynamic covalent cross-linked network is considered to be a dynamic covalent cross-linked network with strong dynamics when it contains two or more dynamic covalent bonds and all dynamic covalent bonds are dynamic covalent bonds with strong dynamics.

In the present invention, the term "non-covalent crosslinking" refers to a crosslinked structure formed by a combination of non-covalent action and a common covalent bond, and the degree of crosslinking of the common covalent crosslinks in the crosslinked network is below the gel point (including the absence of the common covalent crosslinks in the crosslinked network), and the crosslinking formed by the non-covalent action is a necessary condition for forming the crosslinked network; based on the reversible characteristic of the non-covalent crosslinking/supermolecular crosslinking, the formed crosslinked network can carry out dissociation-bonding balance of the crosslinked network under proper conditions, and the dynamic reversibility is shown. The crosslinked network formed by non-covalent crosslinking is the non-covalent crosslinked network. It should be noted that when two or more types of non-covalent interactions are contained in the non-covalent cross-linked network and at least one type of non-covalent interactions is a weak dynamic non-covalent interaction, it is regarded as a weak dynamic non-covalent cross-linked network; a non-covalent cross-linked network is considered to be a strongly dynamic non-covalent cross-linked network when it contains two or more non-covalent interactions and all non-covalent interactions are strongly dynamic non-covalent interactions.

In the present invention, the term "hybrid crosslinking" refers to a crosslinked structure formed by common covalent bonds and dynamic units (including dynamic covalent bonds and non-covalent interactions described in the present invention) together, and the degree of crosslinking of common covalent crosslinks contained in a crosslinked network is above the gel point. The degree of crosslinking by dynamic crosslinking may be at least the gel point or at most the gel point. The cross-linked network formed by the hybridization cross-linking is the hybridization cross-linked network. The hybrid crosslinking network contains common covalent crosslinking and dynamic crosslinking, and is more beneficial to maintaining stable structure in the process of dynamic and reversible transformation of dilatant polymer and material damage repair. Particularly, when the dynamic crosslinking in the hybrid crosslinking network, particularly the degree of crosslinking of weak dynamic crosslinking is above the gel point, dynamic reversible transformation can be generated under specific dynamic stimulation conditions, and the polymer is provided with a shape memory function through the synergistic effect of common covalent crosslinking and dynamic crosslinking, so that the application range of the dilatant material can be widened.

In the invention, the hybrid dynamic crosslinking refers to a crosslinking structure formed by the joint participation of dynamic covalent bonds and non-covalent bonds as well as common covalent bonds, and the crosslinking degree of common covalent crosslinking in a crosslinking network is below the gel point (common covalent crosslinking does not exist in the crosslinking network), and the hybrid dynamic crosslinking in the crosslinking network is a necessary condition for forming the crosslinking network; based on the reversible characteristic of the hybrid dynamic crosslinking, the formed crosslinked network can carry out dissociation-bonding balance of the crosslinked network under proper conditions, and the dynamic reversibility is shown. The cross-linked network formed by the hybrid dynamic cross-linking is the hybrid dynamic cross-linked network. In embodiments of the present invention, when hybrid dynamic crosslinking is present, the respective degrees of crosslinking of the various dynamic crosslinking effects may be above or below the gel point, but the sum of the degrees of crosslinking of the various dynamic crosslinking must be above the gel point of the overall crosslinking system. The dynamic covalent bond and the non-covalent function are simultaneously introduced into the same crosslinking network, so that the prepared dilatant polymer is endowed with richer and orthogonal stimulus responsiveness, and the advantages of the prepared dilatant polymer can be fully exerted by combining different dynamic covalent bonds and the non-covalent functions, the performance of the material can be improved, and the synergistic self-repairing process can be realized by the richer dynamic stimulus function when the material is damaged, so that the damage repair of the material is better realized; in particular, by using two kinds of dynamic crosslinking effects having orthogonality in combination, by reasonably controlling the dynamic stimulus effects, it is also helpful to realize shape memory of the material in addition to providing dynamic reversibility. It should be noted that when the hybrid dynamic crosslinked network contains at least one weak dynamic covalent bond and/or at least one weak dynamic non-covalent effect, the hybrid dynamic crosslinked network is regarded as a weak dynamic hybrid dynamic crosslinked network; when the dynamic covalent bond and the non-covalent function contained in the hybrid dynamic cross-linked network have strong dynamic property, the hybrid dynamic cross-linked network is regarded as the hybrid dynamic cross-linked network with strong dynamic property.

In the present invention, the dynamic unit includes the dynamic covalent bond and non-covalent interactions. Dynamic crosslinking includes the dynamic covalent crosslinking, non-covalent crosslinking and hybrid dynamic crosslinking. Wherein the strong dynamic cross-linking comprises the strong dynamic covalent cross-linking, the strong dynamic non-covalent cross-linking and the strong dynamic hybridization dynamic cross-linking; the weak dynamic cross-linking includes the weak dynamic covalent cross-linking, weak dynamic non-covalent cross-linking and weak dynamic hybrid dynamic cross-linking.

In the present invention, the degree of crosslinking of a component dynamic crosslinking (including dynamic covalent crosslinking, weakly dynamic covalent crosslinking, strongly dynamic covalent crosslinking, non-covalent crosslinking, weakly dynamic non-covalent crosslinking, strongly dynamic non-covalent crosslinking, hybrid dynamic crosslinking, weakly dynamic hybrid dynamic crosslinking) in a dynamic crosslinked network is above the gel point, meaning that when only common covalent bonds are present in the crosslinked network with such components, the crosslinked network remains, and when such components dissociate, the crosslinked network degrades, which may break down 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.

In the present invention, the dilatant hybrid dynamic polymer may contain only one crosslinked network (single network structure) or may contain at least two crosslinked networks (multi-network structure). It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

In the invention, the dilatant hybrid dynamic polymer with a single network structure can be a common covalent cross-linked network and a hybrid cross-linked network, wherein the degree of cross-linking of the common covalent cross-linked in the cross-linked network is above a gel point; the single network structure contains at least one vitrified dilatant polymer component to obtain vitrified dilatant. The single network structure may optionally further comprise dynamic dilatant based on a dynamic dilatant polymer composition, entanglement dilatant based on an entanglement dilatant polymer composition, dispersive dilatant based on a dispersive dilatant composition, and aerodynamic dilatant based on an aerodynamic dilatant structure to enrich dilatant of the dilatant polymer.

In the present invention, the dilatant hybrid dynamic polymer having a multi-network structure may be formed by blending two or more cross-linked networks, may be formed by interpenetration of two or more cross-linked network portions, or may be formed by combination of three or more cross-linked networks, but the present invention is not limited thereto. In the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms with at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a common covalent cross-linked network and a hybrid dynamic cross-linked network, a combination of a hybrid cross-linked network and a dynamic covalent cross-linked network, a combination of a hybrid cross-linked network and a non-covalent cross-linked network, a combination of a hybrid cross-linked network and a hybrid dynamic cross-linked network, a combination of two hybrid cross-linked networks. Wherein, the crosslinking degree of each crosslinking network contained in the dilatant hybrid dynamic polymer can be the same or different; when the degree of crosslinking is different, the network with the highest degree of crosslinking is the first network, and so on.

In the invention, the dilatant hybrid dynamic polymer with the multi-network structure comprises at least one crosslinked network which contains a vitrified dilatant polymer component so as to obtain vitrified dilatant, and preferably each crosslinked network has the vitrified dilatant polymer component; the vitreous dilatant polymer component in each crosslinked network may be the same or different. The structure of the polymer is more controllable, the glass transition temperature of the dilatant polymer is easier to regulate and control, the mutual blending and interpenetration among various networks are facilitated, and better mechanical strength and modulus are obtained; the latter can be used by combining different vitrification dilatant polymer components to obtain dilatant polymers with different glass transition temperatures and larger temperature span in the glass transition process, so that dilatant polymers can be obtained in a wider temperature range. The partially or fully crosslinked network of the dilatant hybrid dynamic polymer with the multi-network structure also optionally contains dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant components and pneumatic dilatant based on pneumatic dilatant structures so as to enrich dilatant of the dilatant polymer.

In the invention, the mechanical property, the dilatant property, the dynamic property and other using properties of the polymer can be regulated and controlled by reasonably designing the dilatant hybrid dynamic polymer crosslinked network structure. When the polymer contains only one crosslinked network, the structure is relatively simple and easy to prepare. In addition, based on the characteristics of a single network structure, the polymer structure can be conveniently regulated and controlled, and the polymer with single controllable glass transition temperature dilatant is also easy to obtain, so that the temperature controllability of the polymer dilatant process is improved (namely, the dilatant process can be realized in a narrower temperature range). When the polymer contains two or more than two cross-linked networks, the networks can be mutually inserted or partially mutually inserted or mutually blended and combined together, so that the mechanical strength and modulus of the dilatant material can be greatly improved, and the dilatant polymer gel or dilatant polymer foam has unique advantages in preparing high-strength dilatant polymer gel or dilatant polymer foam. The reasonable design of the multi-network structure can fully exert the functions of different polymer matrixes and different dynamic crosslinking, and the hybridization/combination/mixing of various dilatant structural factors and component factors, so that the dilatant hybrid dynamic polymer with multiple dilatant can be conveniently obtained, and the requirements of different application scenes on dilatant performance can be better met. In addition, through reasonable design of the multi-network structure, such as design and combination of proper dynamic units, the polymer is provided with shape memory performance together with common covalent crosslinking, and the existence of dynamic crosslinking is also helpful to realize super toughness, further widens the application field of the dilatant material, and the invention and the novelty are also embodied.

In an embodiment of the present invention, the non-crosslinked structure dispersed or blended in the crosslinked network of the dilatant hybrid dynamic polymer is preferably a non-crosslinked dilatant polymer, more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic covalent bond and/or strong dynamic non-covalent effect, which facilitates obtaining additional dynamic dilatant, and also facilitates viscous flow through its segments, further enhancing energy absorbing properties.

By way of example, the dilatant hybrid dynamic polymer according to the present invention has the following preferred cross-linked structure, but the present invention is not limited thereto.

In a preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in side chains and/or side groups of the cross-linked network, and the dynamic covalent bond and the non-covalent function have weak dynamic property. In this embodiment, the dilatancy is a vitrification dilatancy caused by glass transition of the polymer, and is high in sensitivity to temperature, and shows good temperature responsiveness and reliability. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in side chains and/or side groups of the cross-linked network, and the at least one dynamic covalent bond or the non-covalent function has strong dynamic property. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in side chains and/or side groups of the cross-linked network, and the dynamic covalent bond and the non-covalent function have weak dynamic property. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in side chains and/or side groups of the cross-linked network, and the dynamic covalent bond and the non-covalent function have weak dynamic property. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of the cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in side chains and/or side groups of the cross-linked network, and the at least one dynamic covalent bond or the non-covalent function has strong dynamic property. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of the cross-linked network, and the at least one dynamic covalent bond or the non-covalent function has strong dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of the cross-linked network, and the at least one dynamic covalent bond or the non-covalent function has strong dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of the cross-linked network, and the at least one dynamic covalent bond or the non-covalent function has strong dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. Dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the non-crosslinked polymer is also blended and dispersed in the crosslinked network, the non-crosslinked polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a common covalent cross-linked network; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of the cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the crosslinked network does not contain vitrification dilatant polymer components, but is blended and dispersed with non-crosslinked vitrification dilatant polymer. In this embodiment, the dilatancy is a vitrification dilatancy caused by glass transition of the polymer, and is high in sensitivity to temperature, and shows good temperature responsiveness and reliability. The existence of common covalent cross-linking above the gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic units in the crosslinked network can be used as sacrificial bonds to absorb energy and improve toughness and damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property. In this embodiment, the dilatancy is a vitrification dilatancy caused by glass transition of the polymer, and is high in sensitivity to temperature, and shows good temperature responsiveness and reliability. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property; the degree of crosslinking of the weak dynamic crosslinking in the crosslinked network is above the gel point. In this embodiment, the dilatancy is a vitrification dilatancy caused by glass transition of the polymer, and is high in sensitivity to temperature, and shows good temperature responsiveness and reliability. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance. The common covalent crosslinking in the crosslinking network has good structural stability, and the weak dynamic crosslinking has dynamic reversibility under the action of specific dynamic stimulus, and the weak dynamic crosslinking and the weak dynamic crosslinking cooperate to provide the shape memory function for the polymer.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the crosslinked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repairing of material damage, can be used as a sacrificial bond to absorb energy, improve toughness and damage resistance, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microcosmic self-repairing of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the crosslinked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repairing of material damage, can be used as a sacrificial bond to absorb energy, improve toughness and damage resistance, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microcosmic self-repairing of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repairing of material damage, can be used as a sacrificial bond to absorb energy, improve toughness and damage resistance, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microcosmic self-repairing of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repairing of material damage, can be used as a sacrificial bond to absorb energy, improve toughness and damage resistance, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microcosmic self-repairing of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a hybrid cross-linked network; the crosslinked network contains at least one vitrified dilatant polymer component; the cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the cross-linked network is also blended and dispersed with a non-cross-linked polymer, and the non-cross-linked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. Common covalent crosslinking above the gel point contained in the crosslinked network can ensure that even if all dynamic units contained in the polymer undergo dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The weak dynamic crosslinking in the crosslinking network can realize molecular level and microcosmic self-repair of material damage, and can be used as a sacrificial bond to absorb energy, improve toughness and improve damage resistance. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the at least one contained dynamic covalent bond or the non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. A plurality of dynamic units are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material. The introduction of at least one high dynamic element can not only provide dynamic and dynamic dilatancy, but also accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the at least one contained dynamic covalent bond or the non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. A plurality of dynamic units are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one high dynamic element can not only provide dynamic and dynamic dilatancy, but also accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the at least one contained dynamic covalent bond or the non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. A plurality of dynamic units are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one high dynamic element can not only provide dynamic and dynamic dilatancy, but also accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network, and the at least one contained dynamic covalent bond or the non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. A plurality of dynamic units are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one high dynamic element can not only provide dynamic and dynamic dilatancy, but also accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two common covalent cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, wherein the contained dynamic covalent bond and the non-covalent function exist in a side chain and/or a side group of a cross-linked network; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two common covalent cross-linked networks can provide continuous structural stability and excellent mechanical strength for the polymer, so that the dilatant material has high use safety. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid crosslinking network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The hybrid crosslinking network simultaneously introduces weak dynamic covalent bond and non-covalent effect, can endow the polymer with weak dynamic property and abundant stimulus responsiveness, and can also be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. Various dynamic crosslinks are introduced into the hybrid crosslinking network simultaneously, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and the hybrid crosslinking network can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid crosslinking network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The hybrid crosslinking network simultaneously introduces weak dynamic covalent bond and non-covalent effect, can endow the polymer with weak dynamic property and abundant stimulus responsiveness, and can also be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid crosslinking network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The hybrid crosslinking network simultaneously introduces weak dynamic covalent bond and non-covalent effect, can endow the polymer with weak dynamic property and abundant stimulus responsiveness, and can also be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid crosslinking network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The hybrid crosslinking network simultaneously introduces weak dynamic covalent bond and non-covalent effect, can endow the polymer with weak dynamic property and abundant stimulus responsiveness, and can also be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. Various dynamic crosslinks are introduced into the hybrid crosslinking network simultaneously, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and the hybrid crosslinking network can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. Various dynamic crosslinks are introduced into the hybrid crosslinking network simultaneously, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and the hybrid crosslinking network can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid crosslinking network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The hybrid crosslinking network simultaneously introduces weak dynamic covalent bond and non-covalent effect, can endow the polymer with weak dynamic property and abundant stimulus responsiveness, and can also be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. Various dynamic crosslinks are introduced into the hybrid crosslinking network simultaneously, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and the hybrid crosslinking network can be used as a sacrificial bond for absorbing energy and improving the toughness of the material; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a hybridization crosslinking network; the hybrid cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant. The two crosslinking networks are combined together in an interpenetrating or partially interpenetrating way, so that the mechanical strength and modulus of the dilatant material can be greatly improved, the dilatant polymer gel or dilatant polymer foam with high strength can be conveniently prepared, the common covalent crosslinking network and the weak dynamic hybridization dynamic crosslinking network cooperate to play respective structural and performance characteristics, for example, the common covalent crosslinking has good structural stability, the weak dynamic hybridization dynamic crosslinking has weak dynamic property and abundant stimulus responsiveness, the molecular level and microcosmic self-repairing of material damage can be realized, and the dilatant polymer gel or dilatant polymer foam can be used as a sacrificial bond to absorb energy and obtain a shape memory function.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinking networks are combined together in an interpenetrating or partially interpenetrating way, so that the mechanical strength and modulus of the dilatant material can be greatly improved, the dilatant polymer gel or dilatant polymer foam with high strength can be conveniently prepared, the common covalent crosslinking network and the weak dynamic hybridization dynamic crosslinking network cooperate to play respective structural and performance characteristics, for example, the common covalent crosslinking has good structural stability, the hybridization dynamic crosslinking has dynamic property and rich stimulus responsiveness, the molecular level and microscopic self-repairing of material damage can be realized, the dilatant polymer gel or dilatant polymer foam can be used as a sacrificial bond to absorb energy and obtain a shape memory function, the strong dynamic crosslinking can accelerate the microscopic self-repairing of material damage besides providing dynamic property and dynamic dilatant property, and the tear resistance of the material is improved.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The common covalent crosslinking network and the weak dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical properties for the polymer, exert respective structural and performance characteristics, enrich material use performance and improve energy absorption performance of the material, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The common covalent crosslinking network and the weak dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical properties for the polymer, exert respective structural and performance characteristics, enrich material use performance and improve energy absorption performance of the material, and the strong dynamic crosslinking not only provides dynamic property and dynamic dilatancy, but also can accelerate microscopic self-repair of material damage, improve tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material. The strong dynamic crosslinking not only provides dynamic and dynamic dilatancy, but also accelerates microscopic self-repair of material damage, improves tear resistance of the material, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a weak dynamic hybrid dynamic crosslinking network; the weak dynamic hybrid dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The common covalent cross-linking network and the weak dynamic hybridization dynamic cross-linking network cooperate to provide excellent mechanical properties for the polymer, and can also exert respective structural and performance characteristics, enrich the service performance of the material and improve the energy absorption performance of the material. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a strong dynamic hybridization dynamic crosslinking network; the strong dynamic hybridization dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The common covalent crosslinking network and the strong dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking has good structural stability, can provide structural stability when the strong dynamic hybrid dynamic crosslinking is in dynamic reversible transformation, and can avoid material disintegration, and the strong dynamic hybrid dynamic crosslinking has strong dynamic property, besides providing dynamic dilatancy, the material damage can be rapidly and microscopically self-repaired.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a strong dynamic hybridization dynamic crosslinking network; the strong dynamic hybridization dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer comprises vitrified dilatant, dynamic dilatant and entanglement dilatant. The common covalent crosslinking network and the strong dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking has good structural stability, can provide structural stability when the strong dynamic hybrid dynamic crosslinking is in dynamic reversible transformation, and can avoid material disintegration, and the strong dynamic hybrid dynamic crosslinking has strong dynamic property, besides providing dynamic dilatancy, the material damage can be rapidly and microscopically self-repaired.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a strong dynamic hybridization dynamic crosslinking network; the strong dynamic hybridization dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The common covalent crosslinking network and the strong dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking has good structural stability, can provide structural stability when the strong dynamic hybrid dynamic crosslinking is in dynamic reversible transformation, and can avoid material disintegration, and the strong dynamic hybrid dynamic crosslinking has strong dynamic property, besides providing dynamic dilatancy, the material damage can be rapidly and microscopically self-repaired.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a strong dynamic hybridization dynamic crosslinking network; the strong dynamic hybridization dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The common covalent crosslinking network and the strong dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking has good structural stability, can provide structural stability when the strong dynamic hybrid dynamic crosslinking is in dynamic reversible transformation, and can avoid material disintegration, and the strong dynamic hybrid dynamic crosslinking has strong dynamic property, besides providing dynamic dilatancy, the material damage can be rapidly and microscopically self-repaired.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the crosslinking networks is a common covalent crosslinking network, and the other crosslinking network is a strong dynamic hybridization dynamic crosslinking network; the strong dynamic hybridization dynamic cross-linked network contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The common covalent crosslinking network and the strong dynamic hybrid dynamic crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking has good structural stability, can provide structural stability when the strong dynamic hybrid dynamic crosslinking is in dynamic reversible transformation, and can avoid material disintegration, and the strong dynamic hybrid dynamic crosslinking has strong dynamic property, besides providing dynamic dilatancy, the material damage can be rapidly and microscopically self-repaired.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, which is highly sensitive to temperature and exhibits good temperature responsiveness and reliability. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The polymer is introduced with weak dynamic crosslinking action, and can be used as a sacrificial bond to absorb energy and obtain a shape memory function.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one strong dynamic non-covalent effect; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy and obtain a shape memory function; the introduction of strong dynamic non-covalent crosslinking not only provides dynamic and dynamic dilatancy, but also accelerates microscopic self-repair of material damage, improves tear resistance of the material and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic covalent cross-linked network; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the cross-linked network is also blended and dispersed with a non-cross-linked polymer, and the non-cross-linked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the contained dynamic crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a dynamic covalent cross-linked network with strong dynamic property; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The hybrid crosslinking network and the strong dynamic covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a dynamic covalent cross-linked network with strong dynamic property; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer comprises vitrified dilatant, dynamic dilatant and entanglement dilatant. The hybrid crosslinking network and the strong dynamic covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a dynamic covalent cross-linked network with strong dynamic property; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The hybrid crosslinking network and the strong dynamic covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a dynamic covalent cross-linked network with strong dynamic property; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The hybrid crosslinking network and the strong dynamic covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a dynamic covalent cross-linked network with strong dynamic property; the hybrid cross-linked network contains at least one non-covalent function; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The hybrid crosslinking network and the strong dynamic covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, which is highly sensitive to temperature and exhibits good temperature responsiveness and reliability. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The polymer is introduced with weak dynamic crosslinking action, and can be used as a sacrificial bond to absorb energy and obtain a shape memory function.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid cross-linked network contains at least one dynamic covalent bond with strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy and obtain a shape memory function; the high dynamic covalent crosslinking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, and the polymer can be used as a sacrificial bond to absorb energy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The weak dynamic crosslinking effect is introduced into the polymer, so that the polymer can be used as a sacrificial bond to absorb energy; the high dynamic cross-linking is introduced, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a weak dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the cross-linked network is also blended and dispersed with a non-cross-linked polymer, and the non-cross-linked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two crosslinked networks cooperate to provide excellent mechanical strength and material toughness for the polymer, the non-covalent crosslinked network can improve microscopic self-repairing performance, and the existence of common covalent crosslinking above a gel point can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the polymer has high use safety. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a strong dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The hybrid crosslinking network and the strong dynamic non-covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic non-covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repair on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a strong dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer comprises vitrified dilatant, dynamic dilatant and entanglement dilatant. The hybrid crosslinking network and the strong dynamic non-covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and common covalent crosslinking above a gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic non-covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a strong dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The hybrid crosslinking network and the strong dynamic non-covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and common covalent crosslinking above a gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic non-covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a strong dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The hybrid crosslinking network and the strong dynamic non-covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and the common covalent crosslinking above the gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic non-covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repair on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a strong dynamic non-covalent cross-linked network; the hybrid crosslinked network contains at least one dynamic covalent bond; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The hybrid crosslinking network and the strong dynamic non-covalent crosslinking network cooperate to provide excellent mechanical strength and tear resistance, and common covalent crosslinking above a gel point has good structural stability, so that the structural stability can be provided when the contained dynamic crosslinking is subjected to dynamic reversible transformation, the material disintegration is avoided, and the strong dynamic non-covalent crosslinking not only provides dynamic dilatancy, but also can carry out rapid microscopic self-repairing on the damage of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dynamic units contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dilatant hybrid dynamic polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety. The introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dynamic units contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dynamic units contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dynamic units contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dilatant hybrid dynamic polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety. The introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dilatant hybrid dynamic polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety. The introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dynamic units contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dilatant hybrid dynamic polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety. The introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two cross-linked networks; one of the cross-linked networks is a hybrid cross-linked network, and the other cross-linked network is a hybrid dynamic cross-linked network; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two crosslinked networks are combined together in an interpenetrating or partially interpenetrating way, so that excellent mechanical properties are obtained. The crosslinking effect of the hybrid dynamic crosslinking network has dynamic reversibility, can carry out molecular level and microcosmic self-repair on polymer damage, can be used as a sacrificial bond to absorb energy and improve the toughness of materials, and the common covalent crosslinking above the gel point contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversibility transformation, the polymer is not disintegrated, so that the hybrid dynamic crosslinking network has high use safety. The introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, which widens the dilatant temperature range, wherein the dynamic dilatant has low temperature sensitivity, and can avoid the problem of rapid dilatant drop at low temperature. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. A plurality of dynamic cross links are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for energy absorption and material toughness improvement; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one entanglement dilatant polymer component. In this embodiment, the dilatant hybrid dynamic polymer contains both vitrified dilatant and tangled dilatant. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and dispersity dilatant, so that the dilatant hybrid dynamic polymer has higher sensitivity to temperature, better temperature responsiveness and reliability, and the dispersive dilatant composition is introduced, so that the material can be endowed with spike and crack preventing functions, and the practicability of the material is enhanced. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In this embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant and pneumatic dilatant, which is convenient to maintain relatively stable dilatant performance in a wider temperature range, and also helps to shape stability of the dilatant polymer foam, and avoid shrinkage of the foam from affecting dimensional stability of the material. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and dispersive dilatant, so that the dilatant temperature range is widened, the temperature sensitivity of the dynamic dilatant is low, the problem of rapid decrease of the dilatant at low temperature can be avoided, the dispersive dilatant composition is introduced, the material can be endowed with spike and fracture preventing functions, and the practicability of the material is enhanced. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. A plurality of dynamic cross links are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for energy absorption and material toughness improvement; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrification dilatant, dynamic dilatant and pneumatic dilatant, so that the dilatant material can absorb energy effectively in a relatively wide temperature range, and particularly can keep energy absorbing performance at low temperature, and the forming stability of foam can be improved due to the existence of the pneumatic dilatant structure. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. A plurality of dynamic cross links are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for energy absorption and material toughness improvement; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component and at least one dispersive dilatant component; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant does not drop sharply at low temperature, the existence of the pneumatic dilatant structure can improve the forming stability of foam, and the introduction of the dispersive dilatant composition can also endow the material with spike and fracture preventing functions. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The dilatant hybrid dynamic polymer is simultaneously introduced with weak dynamic covalent bond and non-covalent effect, so that the polymer can be endowed with weak dynamic property and rich stimulus responsiveness, and can be used as a sacrificial bond for absorbing energy and improving the toughness of the material.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer comprises at least one vitrified dilatant polymer component, at least one dynamic dilatant polymer component and at least one dispersive dilatant; the form of the dilatant hybrid dynamic polymer is foam, and the dilatant hybrid dynamic polymer has a pneumatic dilatant structure. In the embodiment, the dilatant hybrid dynamic polymer contains vitrified dilatant, dynamic dilatant, dispersive dilatant and pneumatic dilatant, so that the dilatant hybrid dynamic polymer can fully exert the performance characteristics of various dilatants, enrich the dilatant of materials, especially the dilatant at low temperature, and meanwhile, the existence of a pneumatic dilatant structure can improve the forming stability of foam, introduce dispersive dilatant composition and endow the materials with spike and fracture preventing functions. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. A plurality of dynamic cross links are simultaneously introduced into the dilatant hybrid dynamic polymer, so that the polymer can be endowed with dynamic property and stimulus responsiveness, and can be used as a sacrificial bond for energy absorption and material toughness improvement; the introduction of at least one strong dynamic cross-link can accelerate microscopic self-repair of material damage, improve tear resistance of the material, and the like in addition to providing dynamic and dynamic dilatancy.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises two hybrid cross-linked networks; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The two crosslinking networks contain common covalent crosslinking above gel point, can provide continuous structural stability and excellent mechanical strength for the polymer, and ensures that the dilatant material has high use safety. The non-crosslinked polymer dispersed in the crosslinked network can provide additional dynamic dilatancy, and further enhance energy absorption performance through viscous flow of its segments.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises three crosslinked networks, wherein the three crosslinked networks are a common covalent crosslinked network, a dynamic covalent crosslinked network and a non-covalent crosslinked network respectively; the dynamic covalent bond and the non-covalent effect contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant, and the entanglement dilatant polymer component, the dispersion dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. Three cross-linked networks are combined together in an interpenetrating or partially interpenetrating way, so that the dilatant material with excellent mechanical strength can be obtained; the common covalent crosslinking, the dynamic covalent crosslinking and the non-covalent crosslinking respectively play roles in different crosslinking networks, so that the toughness of the material can be better improved, and the micro self-repairing property of the material can be better improved. The dynamic covalent crosslinking and the non-covalent crosslinking can also be used as sacrificial bonds for energy absorption and damage resistance improvement.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises three crosslinked networks, wherein the three crosslinked networks are a common covalent crosslinked network, a strong dynamic covalent crosslinked network and a weak dynamic non-covalent crosslinked network respectively; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks act synergistically to facilitate the preparation of high strength, high toughness and tear resistant dilatant materials. The common covalent crosslinking, the dynamic covalent crosslinking and the non-covalent crosslinking respectively play roles in different crosslinking networks, and are more beneficial to improving the microscopic self-repairability of the material. The dynamic covalent crosslinking and the non-covalent crosslinking can also be used as sacrificial bonds for energy absorption and damage resistance improvement.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises three crosslinked networks, wherein the three crosslinked networks are a common covalent crosslinked network, a weak dynamic covalent crosslinked network and a strong dynamic non-covalent crosslinked network respectively; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks act synergistically to facilitate the preparation of high strength, high toughness and tear resistant dilatant materials. The common covalent crosslinking, the dynamic covalent crosslinking and the non-covalent crosslinking respectively play roles in different crosslinking networks, and are more beneficial to improving the microscopic self-repairability of the material. The dynamic covalent crosslinking and the non-covalent crosslinking can also be used as sacrificial bonds for energy absorption and damage resistance improvement.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises three crosslinked networks, wherein the three crosslinked networks are a common covalent crosslinked network, a strong dynamic covalent crosslinked network and a strong dynamic non-covalent crosslinked network respectively; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks act cooperatively, so that the dilatant material with excellent tear resistance is convenient to prepare, and the existence of the common covalent crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The dilatant hybrid dynamic polymer contains abundant dynamic units with strong dynamic property, and can be used for rapidly and microscopically self-repairing material damage.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a tri-crosslinked network and at least one crosslinked network is a normal covalent crosslinked network and at least one crosslinked network is a hybrid dynamic crosslinked network; the dynamic covalent bond and the non-covalent effect contained in the dilatant hybrid dynamic polymer have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant, and the entanglement dilatant polymer component, the dispersion dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks provide excellent mechanical properties for the polymer together, and the existence of the common covalent crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, so that the use safety of the material can be improved. Dynamic covalent crosslinking and non-covalent crosslinking contained in the polymer can also be used as sacrificial bonds for energy absorption and damage resistance improvement.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a tri-crosslinked network and at least one crosslinked network is a normal covalent crosslinked network and at least one crosslinked network is a hybrid dynamic crosslinked network; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks provide excellent mechanical properties for the polymer together, and the existence of the common covalent crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, so that the use safety of the material can be improved. Dynamic covalent crosslinking and non-covalent crosslinking contained in the polymer can also be used as sacrificial bonds for energy absorption and damage resistance improvement. The introduction of strong dynamic crosslinking not only provides dynamic and dynamic dilatancy, but also accelerates microscopic self-repair of material damage, improves tear resistance of the material, and the like.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a tri-crosslinked network and at least one of the crosslinked networks is a hybrid crosslinked network; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the at least one contained dynamic covalent bond or non-covalent function has strong dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component and at least one dynamic dilatant polymer component; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks provide excellent mechanical properties for the polymer together, and the common covalent crosslinking effect of gel points contained in the hybrid crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, and the use safety of the material can be improved. The introduction of strong dynamic crosslinking not only provides dynamic and dynamic dilatancy, but also accelerates microscopic self-repair of material damage, improves tear resistance of the material, and the like.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a tri-crosslinked network and at least one of the crosslinked networks is a conventional covalent crosslinked network; the dilatant hybrid dynamic polymer contains at least one dynamic covalent bond and at least one non-covalent function, and the contained dynamic covalent bond and the non-covalent function have weak dynamic property; the dilatant hybrid dynamic polymer contains at least one vitrified dilatant polymer component; the dilatant hybrid dynamic polymer is also blended and dispersed with a non-crosslinked polymer, and the non-crosslinked polymer contains at least one dynamic unit with strong dynamic property; the dilatant hybrid dynamic polymer also optionally contains entanglement dilatant polymer components, dispersive dilatant compositions and aerodynamic dilatant structures. In the embodiment, the dilatant hybrid dynamic polymer at least contains vitrified dilatant and dynamic dilatant, and the entanglement dilatant polymer component, the dispersity dilatant composition and the pneumatic dilatant structure which are selectively contained can further enrich the dilatant of the material and better adapt to the dilatant requirements of different application scenes on the material. The three crosslinking networks provide excellent mechanical properties for the polymer together, and the existence of the common covalent crosslinking network can ensure that even if all dynamic units contained in the polymer are subjected to dynamic reversible transformation, the polymer is not disintegrated, so that the use safety of the material can be improved.

In addition to the preferred embodiments described above, the dilatant hybrid dynamic polymer of the present invention can also have a wide variety of other topological compositions. Particularly, the foregoing various preferred network structures of the dilatant hybrid dynamic polymer, especially the common covalent crosslinked network, the hybrid crosslinked network, and the weakly dynamic crosslinked network (including the weakly dynamic covalent crosslinked network, the weakly dynamic non-covalent crosslinked network, and the weakly dynamic hybrid dynamic crosslinked network) may further have a non-crosslinked structure, preferably the non-crosslinked dilatant polymer, and more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic covalent bond and/or strong dynamic non-covalent effect, so that additional dynamic dilatant is conveniently obtained, and the viscous flow of the segment is also facilitated, thereby further improving the energy absorbing performance. Those skilled in the art may implement the logic and context of the present invention reasonably efficiently.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has a very rich energy absorbing mechanism, except the traditional energy absorbing mechanism, the energy absorbing method also comprises the steps of carrying out energy absorption through the dilatancy of the polymer, carrying out energy absorption through dynamic covalent bonds and non-covalent action in the polymer and dynamic reversible transformation processes, and the like as sacrificial bonds, so that the energy absorbing method can provide excellent energy absorbing performance for the polymer energy absorbing material and carry out effective energy absorbing and impact resisting protection, thereby solving the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

In the present invention, the dynamic covalent bond includes a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond.

In the invention, the dynamic covalent bond contains boron atoms in the dynamic structural composition, and the dynamic structural composition comprises fifteen types of bonds including organic boron anhydride bonds, inorganic boron anhydride bonds, organic-inorganic boron anhydride bonds, saturated five-membered ring organic boric acid ester bonds, unsaturated five-membered ring organic boric acid ester bonds, saturated six-membered ring organic boric acid ester bonds, unsaturated five-membered ring inorganic boric acid ester bonds, saturated six-membered ring inorganic boric acid ester bonds, unsaturated six-membered ring inorganic boric acid ester bonds, organic boric acid monoester bonds, inorganic boric acid monoester bonds, organic boric acid silicon ester bonds and inorganic boric acid silicon ester bonds; wherein, each kind of boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. When the boron-containing dynamic covalent bond is selected from two or more than two of the boron-containing dynamic covalent bonds, the boron-containing dynamic covalent bond can be selected from different structures in the same type of boron-containing dynamic covalent bonds, and can also 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 different structures in different types of boron-containing dynamic covalent bonds are preferred.

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

wherein each boron atom in the organoboron anhydride linkages is attached to at least one carbon atom through a boron carbon linkage, and at least one organic group is attached to a boron atom through the boron carbon linkage;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be bound to form rings, to different boron atoms

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

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

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

wherein Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ 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 an oxygen atom, and Y ₁ 、Y ₂ At least one member selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, boron atoms, silicon atoms, Y ₃ 、Y ₄ At least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a, b, c, d each represents a linkage to Y ₁ 、Y ₂ 、Y ₃ 、Y ₄ The number of connected connections; when Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ Each independently selected from the group consisting of hydrogen atoms fluorine atom, chlorine atom,A, b, c, d =0 when bromine atom and iodine atom; when Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ A, b, c, d =1 when each is independently selected from an oxygen atom and a sulfur atom; when Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ A, b, c, d =2 when each is independently selected from a nitrogen atom and a boron atom; when Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ A, b, c, d =3 when each is independently selected from a silicon atom; different +.>

Can be linked to form a ring, +.>

May also 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 include, for example:

in the embodiment of the present invention, the inorganic boron anhydride bond may be formed by reacting 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 a 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 bond is selected from, but not limited to, the following structures:

wherein Y is ₁ 、Y ₂ 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 an oxygen atom, and Y ₁ 、Y ₂ At least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atomThe method comprises the steps of carrying out a first treatment on the surface of the Wherein the boron atom in the structure 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 the boron carbon bond;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a, b each represent a linkage to Y ₁ 、Y ₂ The number of connected connections; when Y is ₁ 、Y ₂ A and b=0 when each is independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; when Y is ₁ 、Y ₂ Each independently selected from oxygen atom, sulfur atom, a, b=1; when Y is ₁ 、Y ₂ A, b=2 when each is independently selected from a nitrogen atom, a boron atom; when Y is ₁ 、Y ₂ A, b=3 when each is independently selected from a silicon atom; different +.>

Can be linked to form a ring, +.>

May also 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 include, for example:

In the embodiment of the present invention, the organic-inorganic boron anhydride bond may be formed by reacting an organic boric acid moiety and an inorganic boric acid moiety 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 organic-inorganic boron anhydride bond.

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

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

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

May also be linked to form rings including, but not limited to, aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring organoboronic acid ester bond structures include, for example: />

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

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

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

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; />

An aromatic ring of an arbitrary number, preferably a six-membered ring, and having two adjacent carbon atoms in an unsaturated five-membered ring organoborate bond; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted. Typical unsaturated five-membered ring organoboronic acid ester bond structures include, for example:

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

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

Wherein the boron atom is bound to a carbon atom by a boron carbon bond and at least one organic group is bound to the boron atom by the boron carbon bond;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

May also be linked to form rings including, but not limited to, aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronic acid ester bond structures include, for example:

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

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

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

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; />

An aromatic ring representing an arbitrary number, preferably from a six-membered ring, and having two adjacent carbon atoms on the aromatic ring, which are located in an unsaturated six-membered ring organoboronic acid ester bond; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted; different +.>

Can be linked to form a ring, +.>

Or may be connected in a ring. Typical unsaturated six-membered ring organoboronic acid ester bond structures include, for example:

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

In the invention, the boron atom in the structure of the saturated five-membered ring organic borate ester bond, unsaturated five-membered ring organic borate ester bond, saturated six-membered ring organic borate ester bond and unsaturated six-membered ring organic borate ester bond is preferably selected from aminomethyl phenyl group @

* Represents a position attached to a boron atom); the organic boric acid moiety 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 is preferably an aminomethylphenylboric acid (ester) moiety.

Because aminomethyl phenylboronic acid (ester) primitive has higher reactivity when reacting with 1, 2-diol primitive and/or o-diphenol primitive and/or 1, 3-diol primitive and/or 2-hydroxymethyl phenol primitive, the formed boron-containing dynamic covalent bond has stronger dynamic reversibility, can carry out dynamic reversibility reaction under milder neutral condition, can show sensitive dynamic characteristics and obvious energy absorption effect, and can show greater advantages as an energy absorption material.

Typical structures of such boron-containing dynamic covalent bonds to which aminomethylphenyl groups are attached are for example:

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

wherein Y is ₁ Selected from oxygen atoms, sulfur atoms, nitrogen atoms, boron atoms, and silicon atoms;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a represents a linkage to Y ₁ The number of connected connections; when Y is ₁ When selected from oxygen atom and sulfur atom, a=1; when Y is ₁ When selected from nitrogen atom and boron atom, a=2; when Y is ₁ A=3 when selected from silicon atoms; different +.>

Can be linked to form a ring, +.>

May also be linked to form rings including, but not limited to, aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring inorganic borate ester bond structures include, for example:

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 may be introduced into the polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the saturated five-membered ring inorganic borate bond.

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

wherein Y is ₁ Selected from oxygen atoms, sulfur atoms, nitrogen atoms, boron atoms, and silicon atoms;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a represents a linkage to Y ₁ The number of connected connections; when Y is ₁ When selected from oxygen atom and sulfur atom, a=1; when Y is ₁ When selected from nitrogen atom and boron atom, a=2; when Y is ₁ A=3 when selected from silicon atoms; />

An aromatic ring of an arbitrary number, preferably a six-membered ring, and having two adjacent carbon atoms in an unsaturated five-membered ring inorganic borate bond; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted. Typical unsaturated five-membered ring inorganic borate ester bond structures include, for example:

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 the polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the 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 Y is ₁ Selected from oxygen atoms, sulfur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably selected from oxygen atoms;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a represents a linkage to Y ₁ The number of connected connections; when Y is ₁ When selected from oxygen atom and sulfur atom, a=1; when Y is ₁ When selected from nitrogen atom and boron atom, a=2; when Y is ₁ A=3 when selected from silicon atoms; different +.>

Can be linked to form a ring, +.>

May also be linked to form rings including, but not limited to, aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring inorganic borate ester bond structures include, for example:

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 may be introduced into the polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the 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:

wherein Y is ₁ Selected from oxygen atomsA sulfur atom, a nitrogen atom, a boron atom, and a silicon atom;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a represents a linkage to Y ₁ The number of connected connections; when Y is ₁ When selected from oxygen atom and sulfur atom, a=1; when Y is ₁ When selected from nitrogen atom and boron atom, a=2; when Y is ₁ A=3 when selected from silicon atoms; />

An aromatic ring of an arbitrary number, preferably a six-membered ring, and having two adjacent carbon atoms in an unsaturated six-membered ring inorganic borate bond; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted; different +.>

Can be linked to form a ring, +.>

Or may be connected in a ring. Typical examples of the unsaturated six-membered ring inorganic borate bond structure include:

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

In the present 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 attached to at least one carbon atom by a boron carbon bond and at least one organic group is attached to the boron atom by the boron carbon bond; i ₁ Selected from divalent linking groups; i ₂ Selected from the group consisting of double bonds directly to two carbon atoms, trivalent alkenyl groups directly to two carbon atoms

A divalent non-carbon atom, a linker containing at least two backbone atoms; />

An aromatic ring having an arbitrary number of atoms, preferably a six-membered ring; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted; />

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be bound to form rings, different carbon atoms, boron atoms

Can also be connected into a ring or be connected with I ₁ 、I ₂ The substituents (substituents) of (a) together form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof, wherein the organoboronic acid monoester linkages formed after the 6, 7 structure forms a ring are other than the saturated five-membered ring organoboronic acid ester linkages, unsaturated five-membered ring organoboronic acid ester linkages, saturated six-membered ring organoboronic acid ester linkages, and unsaturated six-membered ring organoboronic acid ester linkages described previously. Typical examples of the organoboronic acid monoester bond structure include:

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

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

wherein Y is ₁ ～Y ₁₃ 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 an oxygen atom, and Y ₁ 、Y ₂ ；Y ₃ 、Y ₄ ；Y ₅ 、Y ₆ 、Y ₇ 、Y ₈ ；Y ₉ 、Y ₁₀ 、Y ₁₁ 、Y ₁₂ At least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; y is Y ₁₄ Selected from oxygen atoms, sulfur atoms, nitrogen atoms, boron atoms, and silicon atoms; i ₁ Selected from divalent linking groups; i ₂ Selected from the group consisting of double bonds directly to two carbon atoms, trivalent alkenyl groups directly to two carbon atoms

A divalent non-carbon atom, a linker containing at least two backbone atoms; />

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a to n each represent a linkage to Y ₁ ～Y ₁₄ The number of connected connections; when Y is ₁ ～Y ₁₃ When each is independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a to m=0; when Y is ₁ ～Y ₁₄ Each independently selected from oxygen atomsA to n=1 when the sulfur atom is; when Y is ₁ ～Y ₁₄ A to n=2 when each is independently selected from a nitrogen atom and a boron atom; when Y is ₁ ～Y ₁₄ A to n=3 when each is independently selected from silicon atoms; / >

An aromatic ring having an arbitrary number of atoms, preferably a six-membered ring; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted; different +.>

Can be linked to form a ring, +.>

Can also be connected into a ring or be connected with I ₁ 、I ₂ The substituted atoms (substituents) of (a) together form a ring, and the ring includes but is not limited to an aliphatic ring, an ether ring, a condensed ring and combinations thereof, wherein the inorganic boric acid monoester bond formed after the 5, 6, 7 and 8 are formed into the ring 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 examples of the inorganic boric acid monoester bond structure include:

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

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

Wherein the boron atom is attached to at least one carbon atom by a boron carbon bond and at least one organic group is attached to the boron atom by the boron carbon bond;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

May also be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical examples of the organoboronate silicon ester bond structure include:

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

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

wherein Y is ₁ 、Y ₂ 、Y ₃ 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 an oxygen atom, and Y ₁ 、Y ₂ At least one selected from oxygen atomsA sulfur atom, a nitrogen atom, a boron atom, and a silicon atom;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein a, b, c each represent a linkage to Y ₁ 、Y ₂ 、Y ₃ The number of connected connections; when Y is ₁ 、Y ₂ 、Y ₃ A, b, c=0 when each is independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; when Y is ₁ 、Y ₂ 、Y ₃ Each independently selected from oxygen atom, sulfur atom, a, b, c=1; when Y is ₁ 、Y ₂ 、Y ₃ Each independently selected from nitrogen atom, boron atom, a, b, c=2; when Y is ₁ 、Y ₂ 、Y ₃ Each independently selected from the group consisting of silicon atoms, a, b, c=3; different +.>

Can be linked to form a ring, +.>

May also 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 silicon borate bond may be formed by reacting a silanol group contained in a compound raw material with an inorganic boric acid group, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic silicon borate bond.

The organoboronic acid moieties described in embodiments of the present invention are selected from, but are not limited to, any of the following structures:

wherein K is ₁ 、K ₂ 、K ₃ A monovalent organic group or monovalent organosilicon group directly attached to an oxygen atom through a carbon or silicon atom, selected from any of the following structures: small molecule hydrocarbon groups, small molecule silane groups, and polymer chain residues; k (K) ₄ A divalent organic group or divalent organosilicon group directly linked to two oxygen atoms, which is directly linked to an oxygen atom through a carbon atom or a silicon atom, selected from any one of the following structures: divalent small molecule hydrocarbon groups, divalent small molecule silane groups, divalent polymer chain residues; m is M ₁ ⁺ 、M ₂ ⁺ 、M ₃ ⁺ Is a monovalent cation, preferably selected from Na ⁺ 、K ⁺ 、NH ₄ ⁺ ；M ₄ ²⁺ Is a divalent cation, preferably selected from Mg ²⁺ 、Ca ²⁺ 、Zn ²⁺ 、Ba ²⁺ ；X ₁ 、X ₂ 、X ₃ Halogen atoms, preferably selected from chlorine atoms and bromine atoms; d (D) ₁ 、D ₂ D is a group attached to the boron atom ₁ 、D ₂ Are different and are each independently selected from hydroxyl (-OH), ester (-OK) ₁ ) Salt group (-O) ^- M ₁ ⁺ ) Halogen atom (-X) ₁ ) Wherein K is ₁ 、M ₁ ⁺ 、X ₁ The definition of (1) is consistent with the previous description, and is not repeated here; wherein the boron atom in the structure is required to be connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected with the boron atom through the boron-carbon bond;

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring including, but not limited to, aliphatic, aromatic, ether, condensed, anda combination thereof.

Inorganic boronic acid moieties described in embodiments of the present invention are selected from, but not limited to, the following structures:

wherein W is ₁ 、W ₂ 、W ₃ 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 an oxygen atom, and W ₁ 、W ₂ 、W ₃ At least one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom, wherein x, y, z each represent a linkage to W ₁ 、W ₂ 、W ₃ The number of connected connections; when W is ₁ 、W ₂ 、W ₃ X, y, z=0 when each is independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; when W is ₁ 、W ₂ 、W ₃ X, y, z=1 when each is independently selected from an oxygen atom, a sulfur atom; when W is ₁ 、W ₂ 、W ₃ X, y, z=2 when each is independently selected from a nitrogen atom, a boron atom; when W is ₁ 、W ₂ 、W ₃ X, y, z=3 when each is independently selected from a silicon atom; different +. >

Can be linked to form a ring, +.>

May also 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 embodiments of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate, inorganic boron halide as a raw material.

The 1, 2-diol unit in the embodiment of the invention is ethylene glycol

And residues thereof formed upon loss of at least one non-hydroxylic hydrogen atom in the substituted form;

the 1, 3-diol moieties described in embodiments of the invention are 1, 3-propanediol

And residues thereof formed upon loss of at least one non-hydroxylic hydrogen atom in the substituted form;

for the 1, 2-diol and 1, 3-diol, they may have a linear structure or a cyclic structure.

For linear 1, 2-diol primitive structures, it may be selected from any one or any several of class B structures and their isomeric forms:

class B:

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

class C:

wherein R is ₁ ～R ₃ Is a monovalent group attached to the 1, 2-diol moiety; r is R ₄ ～R ₈ Is a monovalent group attached to the 1, 3-diol moiety;

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; wherein R is ₁ ～R ₈ Each independently selected from any one of the following structures: hydrogen atom, hetero atomA child group, a small molecule hydrocarbon group, a polymer chain residue.

Wherein, each of the isomeric forms B1 to B4 and C1 to C6 is independently selected from any one of position isomerism, conformational isomerism and chiral isomerism.

For a cyclic 1, 2-diol primitive structure, it may be formed by linking two carbon atoms in an ethylene glycol molecule through the same group; wherein the cyclic group structure is a 3-200 membered ring, preferably a 3-10 membered ring, more preferably a 3-6 membered ring, the number of cyclic group structures 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 for example:

for cyclic 1, 3-diol primitive structures, they may be formed by the joining of two carbon atoms in a 1, 3-propanediol molecule through the same group; wherein the cyclic group structure is a 3-200 membered ring, preferably a 3-10 membered ring, more preferably a 3-6 membered ring, the number of cyclic group structures 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 for example:

The ortho-diphenol moiety described in the present invention is ortho-diphenol

And substituted forms thereof, and hybrid forms thereof, and combinations thereof, which are missing at least one non-hydroxyhydrogen atom, suitable ortho-diphenol moiety structures are for example:

in the present inventionThe 2-methylol phenol unit is 2-methylol phenol

And substituted forms thereof, and hybrid forms thereof, and combinations thereof, which are formed upon the loss of at least one non-hydroxyhydrogen atom, suitable 2-hydroxymethylphenol motif structures are, for example:

the mono-alcohol radical in the embodiment of the invention refers to a structural radical comprising a hydroxyl group and a carbon atom directly connected with the hydroxyl group

Wherein the carbon atom may be a non-aromatic carbon atom or an aromatic carbon atom), and in the case where the 1, 2-diol moiety, the o-diphenol moiety, the 1, 3-diol moiety, the 2-hydroxymethylphenol moiety form an unsaturated/saturated five-membered ring organoboronic acid ester bond, an unsaturated/saturated six-membered ring organoboronic acid ester bond, an unsaturated/saturated five-membered ring inorganic boronic acid ester bond, or an unsaturated/saturated six-membered ring inorganic boronic acid ester bond, the mono-ol moiety is not a hydroxyl group in the 1, 2-diol moiety, the o-diphenol moiety, the 1, 3-diol moiety, or the 2-hydroxymethylphenol moiety, the mono-ol moiety may be selected from any hydroxyl group in any suitable di (poly) alcohol compound and/or group, except for this case. Suitable structures containing a monoalcohol moiety can be exemplified by:

The silanol group of the present embodiment refers to a structural group comprising a silicon atom and a hydroxyl group or a group which can be a hydroxyl group bonded to the silicon atom

Wherein Z may be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide, and the like, preferably halogen, alkoxy).

The dynamic covalent bond containing boron 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 catalyst, high temperature, illumination or specific pH, can further improve the preparation efficiency, reduces the limitation of the use environment and expands the application range of the polymer.

In the invention, the boron-free dynamic covalent bond does not contain boron atoms in the dynamic structural composition, and the boron-free dynamic covalent bond comprises, but is not limited to, dynamic continuous sulfur bonds, dynamic continuous selenium bonds, dynamic selenium sulfur bonds, dynamic selenium nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, dynamic covalent bonds based on reversible free radicals, combined exchangeable acyl bonds, dynamic covalent bonds based on steric effect induction, dynamic covalent bonds based on reversible addition fragmentation chain transfer, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyl nitrogen heterocyclic onium, unsaturated carbon-carbon double bonds capable of undergoing olefin cross metathesis reaction, unsaturated carbon-carbon triple bonds capable of undergoing alkyne cross metathesis reaction, dynamic covalent bonds of [2+2] cycloaddition, [4+2] cycloaddition, [4+4] cycloaddition, mercapto-Michael addition dynamic covalent bonds, amine alkene-Michael addition dynamic covalent bonds, dynamic covalent bonds based on triazoline dione-indole, dynamic covalent bonds based on diazacarbene, dynamic covalent bonds based on benzoyl groups, hexahydrotriazine-like dynamic covalent bonds, dynamic triad acid-base covalent bonds, dynamic triad dynamic amine covalent bonds capable of undergoing alkyne cross metathesis reaction; wherein each group of boron-free dynamic covalent bonds can comprise multiple types of boron-free dynamic covalent bond structures. When the boron-free dynamic covalent bond is selected from two or more than two types, the boron-free dynamic covalent bond can be selected from different structures in the same type of dynamic covalent bond in the same group of boron-free dynamic covalent bonds, can also be selected from different structures in different types of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, and can also be selected from different structures in different groups of boron-free dynamic covalent bonds, wherein in order to achieve orthogonal and/or synergistic dynamic performance, the different structures in different groups of boron-free dynamic covalent bonds are preferred.

In the invention, the dynamic continuous sulfur bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, can be activated under certain conditions, and generates dissociation, bonding and exchange reaction of the bond to show dynamic reversible characteristics; 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,

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

/>

in an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of dynamic continuous sulfur bonds includes, but is not limited to, temperature regulation, addition of redox agent, addition of catalyst, addition of initiator, illumination, radiation, microwave, plasma action, pH adjustment, and other modes of action. For example, the dynamic sulfur bond can be broken to form sulfur free radical by heating, so that dissociation and exchange reaction of the dynamic sulfur bond occur, and the dynamic sulfur bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairing property and reworkability. The dynamic continuous sulfur bond can be broken by light to form sulfur free radical, so that dissociation and exchange reaction of disulfide bond can be generated, and the dynamic continuous sulfur bond can be reformed after the light is removed, so that the polymer can obtain self-repairing property and reworkability. Radiation, microwaves and plasmas can generate free radicals in the system to react with dynamic sulfide bonds so as to obtain self-repairability and reworkability. The presence of a catalyst, including but not limited to rhodium tetrakis (triphenylphosphine) hydride, 1, 8-diazabicyclo (5.4.0) undec-7-ene, cuprous chloride, methacrylate-copper complex catalysts, alkyl phosphines (e.g., triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine) can promote the formation and exchange of dynamic disulfide bonds, thereby accelerating the self-healing process and achieving reworkability. In embodiments of the present invention, dynamic reaction of disulfide bonds may also be achieved by adding a redox agent to the system. Wherein the reducing agent can promote dissociation of dynamic continuous sulfur bonds to form sulfhydryl groups, thereby obtaining recoverability and reworkability; the oxidizing agent can promote the formation of dynamic continuous sulfur bonds, thereby obtaining the secondary formability. Wherein the reducing agent comprises, but is not limited to, sodium sulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, alkyl mercaptans (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan and the like), alkyl phosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine and the like) and the like; such oxidizing agents include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinone dioxime, disulfide), and the like. The dynamic polymer can also be self-repaired or recycled by adding an initiator into the system and then generating free radicals under the actions of heating, illumination, radiation, microwaves and plasmas to promote dissociation or exchange of dynamic continuous sulfur bonds. Wherein the initiator includes but is not limited to any one or any several of the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl-methanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutarate; organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably 2, 2-dimethoxy-2-phenyl acetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

In the embodiment of the invention, the dynamic continuous sulfur bond can be formed by oxidative coupling reaction of sulfhydryl groups contained in the compound raw material and bonding reaction of sulfur free radicals, and can also be introduced into the polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing disulfide bonds. Among them, the disulfide bond-containing compound raw material is not particularly limited, and a disulfide bond-containing polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide, sulfur, and mercapto compound are preferable, and a disulfide bond-containing polyol, isocyanate, epoxy compound, alkene, and alkyne are more preferable.

In the invention, the dynamic selenium-connecting bond comprises a dynamic double-selenium bond and a dynamic multi-selenium bond, can be activated under certain conditions, and generates dissociation, bonding and exchange reaction of the bond to show dynamic reversible characteristics; the dynamic selenium connecting bond is selected from the following structures:

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

representing a linkage to a polymer chain, a cross-linked network chain or any other suitable group/moietyAnd (5) connection of the sub. Typical dynamic selenium-linked bond structures can be exemplified by:

In an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of the dynamic selenium bond includes, but is not limited to, temperature regulation, addition of redox agent, addition of catalyst, addition of initiator, irradiation, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-repairing property, recycling recoverability, stimulus response, etc. For example, the dynamic selenium-connecting bond can be broken to form selenium free radical by heating, so that dissociation and exchange reaction of the dynamic bond occur, and the dynamic selenium-connecting bond is reformed and stabilized after cooling, thus the self-repairing property and the reworkability are shown; the polymer containing dynamic bonds can obtain good self-repairing performance through laser irradiation; the self-repairing and reworking property can be obtained by utilizing radiation, microwaves and plasmas to generate free radicals and dynamic selenium-connecting bond in the system. The dynamic polymer can be recycled by adding an oxidation-reduction agent into the system; wherein the reducing agent is capable of promoting dissociation of the dynamic selenium linkage into selenol, such that the dynamic polymer dissociates; the oxidizing agent can oxidize selenol to form dynamic selenium-connecting bond, so as to obtain reworkability. Wherein the reducing agent comprises sodium sulfoxylate, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris (2-carboxyethyl) phosphorus hydrochloride, alkyl thiols (such as methyl thiol, ethyl thiol, propyl thiol, etc.), alkyl phosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the oxidizing agent species include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinone dioxime, disulfide), and the like. The dynamic polymer can also be self-repaired or recycled by adding an initiator into the system and then generating free radicals under the actions of heating, illumination, radiation, microwaves and plasmas to promote dissociation or exchange of dynamic selenium-linked bonds. Wherein the initiator includes but is not limited to any one or any several of the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl-methanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutarate; organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably 2, 2-dimethoxy-2-phenyl acetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

In the embodiment of the invention, the dynamic selenium linkage can be formed by oxidation coupling reaction of selenol contained in the compound raw material and bonding reaction of selenium free radical, and can also be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic selenium linkage. Among them, the starting materials of the compound having a dynamic selenium bond are not particularly limited, and preferably a polyol, isocyanate, epoxy, alkene, alkyne, carboxylic acid, diselenide (e.g., sodium diselenide, diselenide dichloride) having a dynamic selenium bond, more preferably a polyol, isocyanate, epoxy, alkene, alkyne having a dynamic selenium bond.

In the invention, the dynamic selenium-sulfur bond can be activated under a certain condition, and the dissociation, bonding and exchange reaction of the bond occur, so that the dynamic reversible characteristic is shown; the dynamic selenium-sulfur bond disclosed by the invention is at least one of the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

In an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of dynamic selenium-sulfur bond includes, but is not limited to, temperature regulation, addition of redox agent, addition of catalyst, addition of initiator, illumination, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-repairing property, recycling property, stimulus response, etc. For example, the dynamic selenium-sulfur bond can be broken by heating to form sulfur free radicals and selenium free radicals, so that dissociation and exchange reaction of the dynamic bond occur, and the dynamic selenium-sulfur bond is reformed and stabilized after cooling, so that the self-repairing property and the reworkability are shown; the polymer containing the sulfur selenium bond can obtain good self-repairing performance through laser irradiation; self-healing and reworkability can be achieved by generating radicals in the system with dynamic selenium sulfide bonds by radiation, microwaves and plasma. The dynamic polymer can also be recycled by adding a redox agent into the system. Wherein the reducing agent comprises sodium sulfoxylate, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris (2-carboxyethyl) phosphorus hydrochloride, alkyl thiols (such as methyl thiol, ethyl thiol, propyl thiol, etc.), alkyl phosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the oxidizing agent species include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinone dioxime, disulfide), and the like. The dynamic polymer can also be self-repaired or recycled by adding an initiator into the system and then generating free radicals under the actions of heating, illumination, radiation, microwaves and plasmas to promote dissociation or exchange of dynamic selenium-sulfur bonds. Wherein the initiator includes but is not limited to any one or any several of the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl-methanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutarate; organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably 2, 2-dimethoxy-2-phenyl acetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

In the embodiment of the invention, the dynamic selenium-sulfur bond can be formed by oxidative coupling reaction of mercaptan and selenol contained in the compound raw material and bonding reaction of sulfur free radical and selenium free radical, and can also be introduced into the polymer by polymerization/crosslinking reaction between the contained reactive groups by utilizing the compound raw material containing the sulfur-selenium bond. Among them, the sulfur-selenium bond-containing compound raw material is not particularly limited, but a sulfur-selenium bond-containing polyol, isocyanate, epoxy compound, alkene, alkyne, and carboxylic acid are preferable, and a sulfur-selenium bond-containing polyol, isocyanate, epoxy compound, alkene, and alkyne are more preferable.

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

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

representing 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 embodiment of the invention, the certain condition for activating dynamic reversibility of the dynamic selenium-nitrogen bond comprises, but is not limited to, temperature regulation, addition of an acid-base catalyst and other action modes, so that the polymer shows good self-repairing property, recycling recoverability, stimulus response and the like. Wherein, the acid-base catalyst can be selected from the following components: (1) inorganic acid, organic acid and acid salt catalyst. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; the organic acid may be exemplified by methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; salts such as sulfate, bisulfate, hydrogen phosphate and the like can be exemplified. (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 brilliant carbonate. (3) Examples of the group IIA alkali metal and its compound include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Examples of the aluminum metal and the compound thereof include aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrous aluminum oxide and sodium hydroxide, an aluminum alkoxide compound, and the like. (5) Organic compounds, for example, ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride Benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, aldoxime, hydrazine monohydrate, N' -diphenylthiourea, scandium triflate (Sc (OTf) ₃ ) Etc. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the ferric compound include an aqueous ferric trichloride solution, ferric sulfate hydrate, ferric nitrate hydrate and the like. 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 selenium nitrogen bond may be formed by reacting a selenium halide and a pyridine derivative contained in a compound raw material.

In the invention, the acetal dynamic covalent bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioaldol bond, can be activated under certain conditions, and generates bond dissociation, ketal reaction and exchange reaction to show dynamic reversible characteristics; wherein, the said "certain condition" for activating dynamic reversibility of acetal dynamic covalent bond refers to heating, proper acidic water-containing condition, etc. The acetal dynamic covalent bond disclosed by the invention is at least one of the following structures:

Wherein X is ₁ 、X ₂ 、X ₃ 、X ₄ Each independently selected from an oxygen atom, a sulfur atom, a nitrogen atom, preferably from an oxygen atom, a sulfur atom; r is R ₁ 、R ₂ Each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue; r is R ₃ 、R ₄ Each independently selected from a single bond, a heteroatom linker, a divalent or multivalent small molecule hydrocarbyl radical, a divalent or multivalent polymer chain residue;

represents a linkage to a polymer chain, a crosslinked network chain or any other suitable group/atom, wherein different +.>

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 can be exemplified by:

in the embodiment of the invention, the acetal dynamic covalent bond can be dissociated in an acidic aqueous solution, is formed under anhydrous acidic condition, and has good pH stimulus response, so that dynamic reversibility can be obtained through adjustment of 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, pelargonic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzene sulfinic acid, p-methoxybenzoic acid, 1, 4-phthalic acid, 4, 5-difluoro-2-nitrophenylacetic acid, 2-bromo-5-fluorobenzenepropionic 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 an acid vapor, without limitation. The invention can also use the acid in a combined mode in different states, such as the formation of dynamic covalent bonds is promoted by using an organic solution of p-toluenesulfonic acid, and recycling recoverability is obtained by dissociating the dynamic covalent bonds by using an aqueous solution of hydrochloric acid.

In the embodiment of the present invention, the acetal-based 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 the compound raw material, or may be formed by exchange reaction of the acetal-based 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 the compound raw material containing the acetal-based dynamic covalent bond. Among them, the raw materials of the compound containing an acetal-based dynamic covalent bond are not particularly limited, and polyhydric alcohols, polythiols, polyamines, isocyanates, epoxy compounds, olefins, alkynes, and carboxylic acids containing an acetal-based dynamic covalent bond are preferable, and polyhydric alcohols, polyamines, isocyanates, epoxy compounds, olefins, and alkynes containing an acetal-based dynamic covalent bond are more preferable.

In the invention, the dynamic covalent bond based on carbon-nitrogen double bond comprises a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond and a dynamic acylhydrazone bond, which can be activated under certain conditions and generate dissociation, condensation and exchange reactions of the dynamic covalent bond, thereby exhibiting dynamic reversible characteristics; wherein, the "certain condition" for activating dynamic reversibility of a dynamic covalent bond based on a carbon-nitrogen double bond refers to a proper pH water-containing condition, a proper catalyst existence condition, a heating condition, a pressurizing condition and the like. The dynamic covalent bond based on carbon-nitrogen double bond described in the present invention is selected from at least one of the following structures:

Wherein R is ₁ Is a divalent or polyvalent small molecule hydrocarbon group;

representing 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 can be exemplified by:

in an embodiment of the present invention, the suitable pH aqueous conditions for promoting the dissociation and condensation reaction of the carbon-nitrogen double bond-based dynamic covalent bond refer to swelling the dynamic polymer in an aqueous solution of a certain pH or wetting the surface thereof with an aqueous solution of a certain pH such that the carbon-nitrogen double bond-based dynamic covalent bond in the dynamic polymer is dynamically reversible. The aqueous solution can be an aqueous solution, or an organic solution containing water, an oligomer, a plasticizer and an ionic liquid. The pH of the aqueous solution selected varies depending on the type of dynamic covalent bond selected based on carbon-nitrogen double bonds, for example, an acidic solution having a pH of 6.5 or less may be selected for hydrolysis of dynamic benzoyl imide bonds, and an acidic solution having a pH of 4 or less may be selected for hydrolysis of dynamic acylhydrazone bonds.

Wherein the acid-base catalyst used for the dissociation, condensation and exchange reaction of the dynamic covalent bond based on the carbon-nitrogen double bond can be selected from the following: (1) inorganic acid, organic acid and acid salt catalyst. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; the organic acid may be exemplified by methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; salts such as sulfate, bisulfate, hydrogen phosphate and the like can be exemplified. (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 brilliant carbonate. (3) Examples of the group IIA alkali metal and its compound include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Examples of the aluminum metal and the compound thereof include aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrous aluminum oxide and sodium hydroxide, an aluminum alkoxide compound, and the like. (5) Organic compounds such as ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldoxime, hydrazine monohydrate, N' -diphenylthiourea, scandium triflate (Sc (OTf) ₃ ) Etc. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the ferric compound include an aqueous ferric trichloride solution, ferric sulfate hydrate, ferric nitrate hydrate and the like. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.

In the embodiment of the invention, the dynamic covalent bond based on carbon-nitrogen double bond can be formed by condensation reaction of ketone group, aldehyde group, acyl group, amino group, hydrazine group and hydrazide group contained in the compound raw material, and can also 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 them, the compound raw material containing a dynamic covalent bond based on a carbon-nitrogen double bond is not particularly limited, and preferably a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid containing a dynamic covalent bond based on a carbon-nitrogen double bond, more preferably a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne containing a dynamic covalent bond based on a carbon-nitrogen double bond.

In the invention, the dynamic covalent bond based on reversible free radical can be activated under certain conditions to generate free radical, and the dynamic reversible characteristic is shown by the bonding or exchange reaction of the bond; wherein, the said "exchange reaction of dynamic covalent bond based on reversible free radical" refers to the formation of new dynamic covalent bond in other places by intermediate state free radical formed after the dissociation of old dynamic covalent bond in polymer, thereby generating exchange of chain and change of polymer topology structure. The dynamic covalent bond based on reversible free radicals 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 and a sulfur atom;

wherein W is ₁ Each independently selected from the group consisting of a single bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a divalent methyl group and substituents thereof, preferably from the group consisting of a direct bond, an ether group, a thioether group; w in different positions ₁ The structures of which are the same or different;

wherein W is ₂ Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, divalent methyl groups and substituents thereof, preferably from thioether groups, secondary amine groups; different fromW of position ₂ The structures of which are the same or different;

wherein W is ₃ Each independently selected from ether groups, thioether groups, preferably ether groups; w in different positions ₃ The structures of which are the same or different;

wherein W is ₄ Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups, and substituents thereof, preferably from ether groups; w in different positions ₄ The structures of which are the same or different;

wherein V, V 'are each independently selected from carbon, nitrogen, and V, V' at different positions have the same or different structure, and are attached to V, V 'when V, V' is selected from nitrogen

Absence of;

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

Is the number of (3); when Z is a selenium atom or a tellurium atom, k is 1, meaning that there is 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 +.>

Is connected with Z, two->

Is the same or different in structure;

wherein R is ₁ Each independently selected from hydrogen atom, halogen atom, heteroatom group, C _1-20 Hydrocarbyl/heterohydrocarbyl, substituted C _1-20 A substituent formed by a combination of two or more of the above hydrocarbon/heterohydrocarbon groups; r is R ₁ Each independently is preferably selected from hydrogen atom, hydroxy, cyano, carboxyl, C _1-20 Alkyl, C _1-20 Aromatic hydrocarbon radical, C _1-20 Heteroaromatic groups and acyl, acyloxy, amido, oxyacyl, thioacyl, aminoacyl, phenylene groupsSubstituted C _1-20 Hydrocarbyl/heterohydrocarbyl; r is R ₁ Further preferably selected from the group consisting of a hydrogen atom, methyl, ethyl, propyl, butyl, phenyl, hydroxyl, cyano, carboxyl, methyloxyacyl, ethyloxyacyl, propyloxyacyl, butyloxyacyl, methylaminoacyl, ethylaminoacyl, propylaminoacyl, butylaminoacyl;

wherein R is ₂ Each independently selected from any suitable atom (including hydrogen atoms), substituent, substituted polymer chain; each R is ₂ The structures of which are the same or different; when R is ₂ When selected from substituents, they are selected from but not limited to: hydroxy, phenyl, phenoxy, C _1-10 Alkyl, C _1-10 Alkoxy, C _1-10 Alkoxyacyl, C _1-10 Alkyl acyloxy, trimethyl siloxy and triethyl siloxy; wherein the substituent atom or substituent is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent, a heteroatom-containing substituent;

wherein R is ₃ Each independently selected from cyano, C _1-10 Alkoxyacyl, C _1-10 Alkyl acyl, C _1-10 An alkylaminoacyl group, a phenyl group, a substituted phenyl group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group; wherein the substituent atom or substituent is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent, a heteroatom-containing substituent;

wherein R is ¹ 、R ² 、R ³ 、R ⁴ Each independently selected from the group consisting of a hydrogen atom, a halogen atom, a heteroatom group, and a substituent; r is R ¹ 、R ² 、R ³ 、R ⁴ Each independently is preferably selected from a hydrogen atom, a halogen atom, a heteroatom group, C _1-20 Hydrocarbon radicals, C _1-20 Heterohydrocarbyl, substituted C _1-20 Hydrocarbyl or substituted C _1-20 A heterohydrocarbyl group, and a substituent formed by a combination of two or more of the above groups; more preferably from hydrogen atom, hydroxy group, cyano group, carboxyl group, C _1-20 Alkyl, C _1-20 C of heteroalkyl, cyclic structure _1-20 C of alkyl, cyclic structure _1-20 Heteroalkyl, C _1-20 Aromatic hydrocarbon radical, C _1-20 A heteroaromatic group;

Wherein R is ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Each independently selected from any suitable atom (including hydrogen atoms), substituent, substituted polymer chain; when R is ⁵ 、R ⁶ 、R ⁷ 、R ⁸ When each is independently selected from substituents, preferably the substituents are sterically hindered substituents; the substituents having steric effects are selected from, but not limited to: cyano, C _1-20 Alkyl, C _1-20 Cycloalkyl, aryl, heteroaryl, and groups formed by substitution of any of the above groups with any substituent atom or substituent; wherein the substituent atom or substituent is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent, a heteroatom-containing substituent; exemplary sterically hindered substituents include, by way of example and not limitation: cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, pyridinyl, C _1-5 Alkyl-substituted phenyl, C _1-5 Alkoxy-substituted phenyl, C _1-5 Alkylthio-substituted phenyl, C _1-5 Alkylamino-substituted phenyl, cyano-substituted phenyl;

wherein L is each independently selected from the group consisting of heteroatom linkers, heteroatom group linkers, and divalent C _1-20 Hydrocarbyl/heterohydrocarbyl, substituted divalent C _1-20 A divalent linking group formed by a combination of two or more of the above hydrocarbon/heterohydrocarbon groups; wherein the substituent atom or substituent is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent, a heteroatom-containing substituent; l is each independently selected from acyl, acyloxy, alkylthio, amido, oxyacyl, thio, phenylene, and divalent C _1-20 Hydrocarbyl/heterohydrocarbyl, substituted divalent C _1-20 Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C _1-20 The structure of the substituent in the hydrocarbon/heterohydrocarbon group is preferably acyl, acyloxy, alkylthio, amido, oxyacyl, thioacyl, aminoacyl, phenylene, more preferably the substituentIs C of divalent state of (2) _1-20 Hydrocarbyl/heterohydrocarbyl groups linked to R by said substituent groups ₁ Is attached to a carbon atom of (2);

wherein, the liquid crystal display device comprises a liquid crystal display device,

meaning that the ring has a conjugated structure; wherein (1)>

Is a five-membered nitrogen heterocyclic ring structure with a conjugated structure; wherein, the liquid crystal display device comprises a liquid crystal display device,

the two five-membered nitrogen heterocycles form a multi-ring structure formed by carbon-carbon single bonds, carbon-nitrogen single bonds or nitrogen-nitrogen single bonds through one ring-forming atom respectively; according to different connection modes, < > a->

Including but not limited to one or more of the following isomers: / >

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

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

wherein, the liquid crystal display device comprises a liquid crystal display device,

indicating that there are n->

Wherein n is 0, 1 or an integer greater than 1; wherein, the label is the site of attachment to other structures in the formula; said->

Preferably, but not limited to, at least one of the following structures:

the said process

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

/>

wherein, the liquid crystal display device comprises a liquid crystal display device,

is an aromatic ring; the ring structure of the aromatic ring is selected from a single ring structure, a multi-ring structure, a spiro ring structure and a 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, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent or substituents; wherein the substituent atom or substituent is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent, a heteroatom-containing substituent;

wherein, the liquid crystal display device comprises a liquid crystal display device,

indicating that there are n->

Aromatic rings of (C) in different positions +.>

The structures of which are the same or different; wherein, the label is the site of attachment to other structures in the formula;

wherein, the liquid crystal display device comprises a liquid crystal display device,

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; each of which is

The structures are the same or different; different->

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

Typical dynamic covalent bond structures based on reversible free radicals can be exemplified by:

/>

/>

/>

therein, W, W ₁ 、W ₂ 、W ₃ 、W ₄ 、

The definition, selection range, preferred range of (c) are as described above.

In embodiments of the present invention, the "certain conditions" for activating dynamic reversibility of a dynamic covalent bond based on reversible free radicals include, but are not limited to, temperature regulation, addition of an initiator, irradiation, microwave, plasma action, and the like. For example, the dynamic covalent bond can be broken to form free radicals by heating, so that dissociation and exchange reaction of the dynamic covalent bond occur, and the dynamic covalent bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairing property and reworkability. The dynamic covalent bond can be broken by light to form free radicals, so that dissociation and exchange reaction of the dynamic covalent bond occur, and the dynamic covalent bond is reformed after the light is removed, so that the polymer can obtain self-repairing property and reworkability. Radiation, microwaves and plasma can generate free radicals in the system to react with dynamic covalent bonds to obtain self-repairability and reworkability. The initiator can generate free radicals, promote dissociation or exchange of dynamic covalent bonds, and obtain self-repairability or recyclability. Wherein the initiator includes but is not limited to any one or any several of the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl-methanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutarate; organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably 2, 2-dimethoxy-2-phenyl acetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

In an embodiment of the present invention, the dynamic covalent bond based on reversible free radical contained in the polymer may be formed by a bonding reaction of free radical contained in the compound raw material or other suitable coupling reaction; 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 dynamic covalent bonds based on reversible free radicals. Among them, the compound raw material containing a dynamic covalent bond based on a reversible free radical is not particularly limited, and preferably a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid containing a dynamic covalent bond based on a reversible free radical, more preferably a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne containing a dynamic covalent bond based on a reversible free radical.

In the invention, the bonding exchangeable acyl bond can be activated under certain conditions and can generate bonding acyl exchange reaction (such as bonding transesterification reaction, bonding amide exchange reaction, bonding carbamate exchange reaction, bonding vinylogous amide or vinylogous carbamate exchange reaction and the like) with nucleophilic groups, so that the bonding exchangeable acyl bond has dynamic reversible characteristics; wherein, the said "combined acyl exchange reaction" means that the combined exchangeable acyl bond is combined with nucleophilic group to form intermediate structure, and then the acyl exchange reaction is carried out to form new dynamic covalent bond, thereby generating chain exchange and change of polymer topological structure, wherein, the crosslinking degree of the polymer can be kept unchanged; wherein, the said "certain condition" for activating the dynamic reversibility of the binding exchangeable acyl bond refers to the proper catalyst existence condition, heating condition, pressurizing condition, etc.; the "nucleophilic group" refers to active groups such as hydroxyl, sulfhydryl and amino groups which exist in a polymer system and are used for carrying out a combined acyl exchange reaction, and the nucleophilic group can be bonded on the same polymer network/chain with combined exchangeable acyl groups, can be on different polymer networks/chains, and can also be introduced through small molecules and polymers containing nucleophilic groups. The binding exchangeable acyl bond described in the present invention is selected from at least one of the following structures:

Wherein X is ₁ 、X ₂ Selected from the group consisting of 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; z is Z ₁ 、Z ₂ Selected from oxygen atoms and sulfur atoms; r is R ₅ Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, and polymer chain residues; wherein when X is ₁ 、X ₂ When oxygen atom or sulfur atom, R ₁ 、R ₂ 、R ₃ 、R ₄ Absence of; when X is ₁ 、X ₂ R is a nitrogen atom ₁ 、R ₃ In presence of R ₂ 、R ₄ Is absent and R ₁ 、R ₃ Each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue; when X is ₁ 、X ₂ R is a carbon atom or a silicon atom ₁ 、R ₂ 、R ₃ 、R ₄ Are present and are each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue;

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

Among them, a binding exchangeable acyl bond containing a nucleophilic group is more preferable, and typical structures thereof include, for example:

in the present invention, part of the combined acyl exchange reaction needs to be carried out under the condition of a catalyst comprising a catalyst for transesterification reaction (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange reaction (including amides, carbamates, thiocarbamates, ureas, vinylideneamides, etc.). By adding the catalyst, the occurrence of the bonded acyl exchange reaction can be promoted, so that the dynamic polymer exhibits good dynamic characteristics.

Wherein the catalyst used for the transesterification reaction may be selected from: (1) inorganic acid, organic acid and acid salt catalyst. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; the organic acid may be exemplified by methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; salts such as sulfate, bisulfate, hydrogen phosphate and the like can be exemplified. (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 brilliant carbonate. (3) Examples of the group IIA alkali metal and the compound thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, and magnesium ethoxide. (4) Examples of the aluminum metal and the compound thereof include aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrous aluminum oxide and sodium hydroxide, and an aluminum alkoxide compound. (5) Tin compounds, including inorganic and organic tin compounds. Examples of the inorganic tin include tin oxide, tin sulfate, stannous oxide, and stannous chloride. Examples of organotin compounds include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tributyltin acetate, tributyltin chloride and Trimethyltin chloride, and the like. (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) The anionic layered column compound generally comprises hydroxide of two metals, called double metal hydroxide LDH, and the calcined product is LDO, and can be exemplified by hydrotalcite { Mg } ₆ (CO ₃ )[Al(OH) ₆ ] ₂ (OH) ₄ ·4H ₂ O }. (8) Supported solid catalysts, such as KF/CaO, K ₂ CO ₃ /CaO、KF/γ-Al ₂ O ₃ 、K ₂ CO ₃ /γ-Al ₂ O ₃ 、KF/Mg-La、K ₂ O/activated carbon, K ₂ CO ₃ Coal ash powder, KOH/NaX, KF/MMT (montmorillonite) and other compounds. (9) Examples of the organic zinc compound include zinc acetate and zinc acetylacetonate. (10) Organic compounds, for example, 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, and the like. Among them, organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, 2-MI are preferable; more preferably, TBD and zinc acetate are mixed and co-catalyzed, and 2-MI and zinc acetylacetonate are mixed and co-catalyzed.

Wherein the catalyst for amine exchange reaction may be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldoxime, hydrazine monohydrate, N' -diphenylthiourea, scandium triflate (Sc (OTf) ₃ ) Montmorillonite KSF, hafnium tetrachloride (HfCl) ₄ )、Hf ₄ Cl ₅ O ₂₄ H ₂₄ 、HfCl ₄ KSF-polyDMAP, transglutaminase (TGase); a divalent copper compound, for example, copper acetate; examples of the ferric compound include an aqueous ferric trichloride solution, ferric sulfate hydrate, ferric nitrate hydrate and the like. Among them, copper acetate is preferable; sc (OTf) ₃ HfCl ₄ Mixing and co-catalyzing; hfCl ₄ KSF-polyDMAP; the glycerin, boric acid and ferric nitrate hydrate are mixed to share synergistic catalysis.

In embodiments of the present invention, certain of the binding acyl exchange reactions may also be carried out by microwave irradiation, heating. For example, common urethane bonds, thiocarbamate bonds and urea bonds can undergo acyl exchange reaction when heated to 160-180 ℃ with the assistance of a pressure of 4 MPa; the vinyl amide bond and the vinyl carbamate bond can be subjected to an acyl exchange reaction through Michael addition when heated to more than 100 ℃;

the structural carbamate bond can undergo an acyl exchange reaction with a molecular chain containing a phenolic hydroxyl group or a benzyl hydroxyl group structure when heated to more than 90 ℃. The present invention preferably performs the reversible reaction under the usual temperature and usual pressure conditions by adding a catalyst useful for the binding acyl exchange reaction.

In an embodiment of the present invention, the above-mentioned binding exchangeable acyl 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, a hydroxyl group, an amino group, and a mercapto 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 them, the raw material of the compound containing a binding exchangeable acyl bond is not particularly limited, and a polyhydric alcohol, a polyhydric thiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid containing a binding exchangeable acyl bond is preferable, and a polyhydric alcohol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne containing a binding exchangeable acyl bond is more preferable.

In the invention, the dynamic covalent bond based on steric hindrance induction can be activated at room temperature or under certain conditions due to the fact that the dynamic covalent bond contains a large group with steric hindrance, and the dynamic reversible characteristic is shown by dissociation, bonding and exchange reaction of the bond. The steric effect-based induced dynamic covalent bond described in the present invention is selected from at least one of the following structures:

Wherein X is ₁ 、X ₂ Selected from the group consisting of carbon atoms, silicon atoms, and nitrogen atoms, preferably carbon atoms, nitrogen atoms; z is Z ₁ 、Z ₂ Selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X is ₁ 、X ₂ R is a nitrogen atom ₁ 、R ₃ In presence of R ₂ 、R ₄ Is absent and R ₁ 、R ₃ Each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue; when X is ₁ 、X ₂ R is a carbon atom or a silicon atom ₁ 、R ₂ 、R ₃ 、R ₄ Are present and are each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue; wherein R is _b Is a bulky group having steric hindrance and being directly bonded to the nitrogen atom, and may be selected from C _3-20 Alkyl, ring C _3-20 Alkyl, phenyl, benzyl, aralkyl and unsaturated forms of the above groups, substituted forms, hybridized forms, and combinations thereof, more preferably from isopropyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl, most preferably from t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl;

A nitrogen-containing ring of any number, which may be an aliphatic ring or an aromatic ring, which may be an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, each of which is independently selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and other hetero atoms, and a hydrogen atom on the ring-forming atom may be substituted with any substituent or may not be substituted, and a method of producing the sameThe ring is preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a piperidine ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring; n represents the number of links to the ring-forming atoms of the cyclic group structure. Typical steric effect-based induced dynamic covalent bond structures can be exemplified by: />

The large group with steric hindrance effect is directly connected with the nitrogen atom or forms a ring structure with the nitrogen atom, and can weaken the chemical bond strength between the carbon atoms in carbonyl and thiocarbonyl and adjacent nitrogen atoms, so that the carbon-nitrogen bond shows the property of dynamic covalent bond, and the dynamic reversible reaction can be carried out at room temperature or under certain conditions. It is noted that the steric effect in the "bulky group with steric effect" is not as large as good as it is, but is moderate in size, and makes the carbon-nitrogen bond have suitable dynamic reversibility. The "certain condition" for activating dynamic reversibility of dynamic covalent bond induced by steric effect includes but is not limited to the action modes of heating, pressurizing, illumination, radiation, microwave, plasma action and the like, so that the polymer shows good self-repairing property, recycling recoverability, stimulus response and the like. For example, the number of the cells to be processed,

The dynamic covalent bond of the structure can be subjected to dynamic exchange reaction at 60 ℃ to show 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 thiocarbamate bond, steric-effect-induced urea bond.

In an embodiment of the present invention, the steric effect-based induced dynamic covalent bond may be formed by a 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, and an amino group having a large group having a steric effect attached thereto, which are contained in the compound raw material, or may be introduced into the polymer by a polymerization/crosslinking reaction between reactive groups contained therein using the compound raw material having the steric effect-based induced dynamic covalent bond. Among them, the starting materials of the compound containing a steric-effect-induced dynamic covalent bond are not particularly limited, and polyhydric alcohols, polythiols, polyamines, isocyanates, epoxy compounds, olefins, alkynes, and carboxylic acids containing a steric-effect-induced dynamic covalent bond are preferable, and polyhydric alcohols, polyamines, isocyanates, epoxy compounds, olefins, and alkynes containing a steric-effect-induced dynamic covalent bond are more preferable.

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 occurs, so that the reversible addition fragmentation chain transfer dynamic covalent bond has dynamic reversible characteristics. 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 is ₁ ～R ₁₀ Each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group, a polymer chain residue; x is X ₁ 、X ₂ 、X ₃ Each independently selected from single bond, divalent or multivalent small molecule hydrocarbyl, preferably from divalent C _1-20 Alkyl groups and substituted forms thereof, hybridized forms thereof, and combinations thereof, more preferably from the group consisting of divalent isopropyl groups, divalent isopropyl ester groups, divalent isopropyl carboxyl groups, divalent isopropyl nitrile groups, divalent nitrile isopropyl groups, divalent acrylic acid based n-mers, divalent styrene based n-mers and substituted forms thereof, hybridized forms thereof, and combinations thereof, wherein n is 2 or more; z is Z ₁ 、Z ₂ 、Z ₃ Each independently selected from single bond, heteroatom linker, divalent or multivalent small molecule hydrocarbyl, preferably from heteroatom linker having or attached to a group having an electron withdrawing effect, having an electron withdrawing effect Divalent or polyvalent small molecule hydrocarbon groups to which groups having an electron withdrawing effect should be attached; wherein as Z ₂ 、Z ₃ It may be selected from the group consisting of ether group, thio group, seleno group, divalent silicon group, divalent amine group, divalent phosphate group, divalent phenyl group, methylene group, ethylene group, divalent styryl group, divalent isopropyl phenyl group, divalent isopropyl ester group, divalent isopropyl carboxyl group, divalent isopropyl nitrile group, and divalent nitrile isopropyl phenyl group; wherein the groups having an electron withdrawing effect include, but are not limited to, carbonyl groups, aldehyde groups, nitro groups, ester groups, sulfonic acid groups, amide groups, sulfone groups, trifluoromethyl groups, aryl groups, cyano groups, halogen atoms, alkene groups, alkyne groups, and combinations thereof;

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

The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is preferably a polyacrylic acid group and its ester group, a polymethacrylic acid group and its ester group, a polystyrene group, a polymethylstyryl group, an allyl sulfide group, a dithioester group, a diselenate group, a trithiocarbonate group, a diseleno carbonate group, a diseleno thiocarbonate group, a dithioseleno carbonate group, a dithioester group, a diseleno ester group, a ditrishiocarbonate group, a ditriseleno carbonate group, a dithiourethane group, a diseleno urethane group, a dithiocarbonate group, a diseleno carbonate group, or a derivative thereof.

Typical reversible addition fragmentation chain transfer dynamic covalent bond structures include, for example:

wherein n is the number of repeating units, which may be a fixed value or an average value, and n is not less than 1.

The term "reversible addition fragmentation chain transfer reaction" as used herein refers to a process wherein a living radical reacts with a reversible addition fragmentation chain transfer dynamic covalent bond as described herein to form an intermediate, the intermediate is capable of cleaving to form a new living radical and form a new reversible addition fragmentation chain transfer dynamic covalent bond, and the process is reversible. This process is similar to, but not exactly identical to, the reversible addition fragmentation chain transfer process in reversible addition fragmentation chain transfer polymerization. First, reversible addition fragmentation chain transfer polymerization is a solution polymerization process, and the "reversible addition fragmentation chain transfer reaction" described in the present invention may be performed in solution or in solid; in addition, in the reversible addition fragmentation chain transfer reaction, a proper amount of a substance capable of generating active free radicals can be added, and the active free radicals can be generated under certain conditions, so that the reversible addition fragmentation chain transfer dynamic covalent bond has good dynamic reversibility, and 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 the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl-methanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutarate; organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably 2, 2-dimethoxy-2-phenyl acetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

In an embodiment of the present invention, the reversible addition fragmentation chain transfer dynamic covalent bond may be introduced into a polymer by a polymerization/crosslinking reaction between 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 generates siloxane exchange reaction to show dynamic reversible property; wherein, the "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere and accompanied by the dissociation of old siloxane bonds, thereby producing exchange of chains and change of polymer topology. The dynamic siloxane bond described in the present invention is selected from the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; />

Which may or may not be looped.

In the present invention, the siloxane reaction is required to be carried out under a catalyst or under heating, wherein the dynamic siloxane bond is preferably a siloxane bond exchange reaction in the presence of a catalyst. The catalyst can promote the siloxane equilibrium reaction to make dynamic polymer show good dynamic property. Wherein the catalyst for siloxane equilibration reaction may 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 alkali metal polyalkoxide include potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutanol, sodium tert-butoxide, potassium tert-butoxide, lithium pentanolate, potassium ethoxide, sodium glycerol, potassium 1, 4-butanediol, sodium 1, 3-propanediol, lithium pentaerythritol, and sodium cyclohexanol. (3) As the silanol salt, potassium triphenylphosphine, sodium dimethylphenyl silanol, lithium tri-t-butoxysilanol, potassium trimethylsilanol, sodium triethylsilanol, (4-methoxyphenyl) lithium dimethylsilanol, tri-t-pentyloxysianol, potassium diphenylsilanediol, benzyl trimethylammonio-bis (catechol) phenylsilanol and the like can be exemplified. (4) Quaternary ammonium bases such as 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-trimethyl-3- (trifluoromethyl) aniline hydroxide, N-ethyl-N hydroxide, N-dimethyl-ethylammonium, tetra-decylammonium hydroxide, tetra-pentylammonium hydroxide, N, N, N-trimethyl-1-adamantylammonium hydroxide, tetra-octaalkylammonium hydroxide, N, N-dimethyl-N- [3- (thiooxo) propyl ] -1-nonanammonium hydroxide inner salt, (methoxycarbonylsulfamoyl) triethylammonium hydroxide, 3-sulfopropyldodecyl dimethyl betaine, 3- (N, N-dimethylpalmitin) propane sulfonate, methacryloylethylsulfobetaine, N, N-dimethyl-N- (3-sulfopropyl) -1-octadecylammonium inner salt, tributyl-methylammonium hydroxide, tri (2-hydroxyethyl) methylammonium hydroxide, tetradecyl sulfobetaine, and the like. In the present invention, the catalyst used for the siloxane equilibrium reaction is preferably a catalyst of quaternary ammonium base type, silanol type or alkali metal hydroxide type, and more preferably a catalyst of lithium hydroxide, potassium trimethylsilanol, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH) or the like.

In an embodiment of the present invention, the dynamic siloxane bond may be formed by condensation reaction between a silicon hydroxyl group and a silicon hydroxyl group precursor contained in the compound raw materialThe compound starting materials containing dynamic siloxane bonds can be utilized to incorporate the polymer by polymerization/crosslinking reactions between the reactive groups they contain. Among them, the starting materials of the compound having a dynamic siloxane bond are not particularly limited, and preferably a polyol, a polyamine, an isocyanate, a siloxane compound, a silicone compound, an epoxy compound, an alkene, or an alkyne having a dynamic siloxane bond, more preferably a polyol, an isocyanate, a siloxane compound, a silicone compound, or an alkene having a dynamic siloxane bond. Wherein the silicon hydroxyl precursor refers to a structural element (Si-X) consisting of a silicon atom and a group which is connected with the silicon atom and can be hydrolyzed to obtain hydroxyl ₁ ) Wherein X is ₁ The group which can be hydrolyzed to give a hydroxyl group may be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide. Suitable silicon hydroxyl precursors are, for example: si-Cl, si-CN, si-CNS, si-CNO, si-SO ₄ CH ₃ ，Si-OB(OCH ₃ ) ₂ ，Si-NH ₂ ，Si-N(CH ₃ ) ₂ ，Si-OCH ₃ ，Si-COCH ₃ ，Si-OCOCH ₃ ，Si-CONH ₂ ，Si-O-N＝C(CH ₃ ) ₂ ，Si-ONa。

In the invention, the dynamic silicon ether bond can be activated under the heating condition and generates the silicon ether bond exchange reaction, thereby showing the dynamic reversible characteristic; wherein, the "silyl ether bond exchange reaction" refers to the formation of new silyl ether bonds elsewhere and accompanied by the dissociation of old silyl ether bonds, thereby producing exchange of chains and change of polymer topology. The dynamic silicon ether bond is selected from the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

representing a polymer chain, a cross-linked network chain, or any other suitable chainA group/atom linkage; />

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

in the embodiment of the present invention, the dynamic silyl ether bond may be formed by condensation reaction of a silicon hydroxyl group and a silicon hydroxyl group precursor contained in the compound raw material with a hydroxyl group in the system, or may be introduced into the polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic silyl ether bond. Among them, the starting materials of the compound containing a dynamic silyl ether bond are not particularly limited, and preferably a polyol, a polyamine, an isocyanate, a silicone compound, a silane compound, an epoxy compound, an alkene, or an alkyne containing a dynamic silyl ether bond, more preferably a polyol, an isocyanate, a silicone compound, a silane compound, or an alkene containing a dynamic silyl ether bond. Wherein the silicon hydroxyl precursor refers to a structural element (Si-X) consisting of a silicon atom and a group which is connected with the silicon atom and can be hydrolyzed to obtain hydroxyl ₁ ) Wherein X is ₁ The group which can be hydrolyzed to give a hydroxyl group may be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide. Suitable silicon hydroxyl precursors are, for example: si-Cl, si-CN, si-CNS, si-CNO, si-SO ₄ CH ₃ ，Si-OB(OCH ₃ ) ₂ ，Si-NH ₂ ，Si-N(CH ₃ ) ₂ ，Si-OCH ₃ ，Si-COCH ₃ ，Si-OCOCH ₃ ，Si-CONH ₂ ，Si-O-N＝C(CH ₃ ) ₂ ，Si-ONa。

In the invention, the exchangeable dynamic covalent bond based on the alkylazacycloonium can be activated under certain conditions and can perform dynamic exchange reaction with the halogenated alkyl, so that the dynamic reversible characteristic is reflected. The exchangeable dynamic covalent bond based on alkylazacycloonium described in the present invention is selected from at least one of the following structures:

/>

wherein X is ^— Is a negative ion selected from bromide, iodide, preferably bromide;

representing a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical exchangeable dynamic covalent bond structures based on alkylazacycloonium can be exemplified by:

in embodiments of the present invention, the haloalkyl groups, which may be aliphatic haloalkyl groups or aromatic haloalkyl groups, may be present in any suitable terminal, pendant, and/or side chains in the dynamic polymer, or in any suitable form in other components such as small molecules, oligomers, etc., may be present in the same polymer network/chain as the alkylazacycloonium-based exchangeable dynamic covalent bonds, may be present in different polymer networks/chains, or may be incorporated by small molecules, polymers containing haloalkyl groups.

In an embodiment of the present invention, the "certain conditions" for activating dynamic reversibility of an exchangeable dynamic covalent bond based on an alkylazacycloonium, which means in the presence of a haloalkyl group and a solvent and under suitable temperature, humidity, pressure conditions, etc.

In an embodiment of the present invention, the alkyl azetidinium-based exchangeable dynamic covalent bond may be formed by the reaction of a triazolyl/pyridyl compound with a halogenated hydrocarbon, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained therein using a compound starting material containing an alkyl azetidinium-based exchangeable dynamic covalent bond. Wherein, the triazole-based compound can be generated by utilizing the reaction of azide groups contained in the compound raw material and alkyne; among them, the halogenated hydrocarbons include, but are not limited to, saturated halogenated hydrocarbons (e.g., methyl chloride, bromocyclohexane, 1, 2-dibromoethane, diiodomethane, etc.), unsaturated halogenated hydrocarbons (e.g., vinyl bromide, 3-chlorocyclohexene, 4-bromo-1-butene-3-alkyne, 1-bromo-2-iodocyclobutene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, β -bromonaphthalene, phenylchloromethane, o-dichlorobenzene, etc.), etc.; among them, the starting materials of the compound containing an exchangeable dynamic covalent bond based on alkylazacycloonium are not particularly limited, and preferably polyols, isocyanates, epoxy compounds, olefins, alkynes, carboxylic acids, esters, and amides containing an exchangeable dynamic covalent bond based on alkylazacycloonium, and more preferably polyols, isocyanates, epoxy compounds, olefins, and alkynes containing an exchangeable dynamic covalent bond based on alkylazacycloonium.

In the present invention, the unsaturated carbon-carbon double bond which can undergo an olefin cross-metathesis reaction can be activated in the presence of a catalyst, and the olefin cross-metathesis reaction occurs, exhibiting a dynamic reversible property; wherein, the olefin cross-metathesis reaction refers to a carbon skeleton rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by a metal catalyst; wherein, the "rearrangement reaction" refers to the generation of new carbon-carbon double bonds elsewhere and accompanied by the dissociation of old carbon-carbon double bonds, thereby producing exchange of chains and change of polymer topology. The structure of the unsaturated carbon-carbon double bond that can undergo olefin cross-metathesis reaction in the present invention is not particularly limited, and a structure having a small steric hindrance and a high reactivity is preferable from the following:

in an embodiment of the invention, the catalyst for catalyzing olefin cross-metathesis reactions includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, and the like; among them, the catalyst is preferably a ruthenium-based, molybdenum-based, tungsten-based catalyst, more preferably a ruthenium catalyst which is more efficient in catalysis and insensitive to air and water, particularly a commercially available catalyst such as Grubbs 'first, second and third generation catalysts, hoveyda-Grubbs' first, second generation catalysts and the like. Examples of catalysts useful in the present invention for catalyzing olefin cross-metathesis reactions include, but are not limited to, the following:

Wherein Py is ₃ Is that

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 which can generate alkyne cross-metathesis reaction can be activated in the presence of a catalyst, and the alkyne cross-metathesis reaction can generate the dynamic reversible characteristic; wherein, the alkyne cross-metathesis reaction refers to a carbon skeleton rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; wherein, the rearrangement reaction refers to the generation of new carbon-carbon triple bonds at other places and the dissociation of old carbon-carbon triple bonds, thereby generating chain exchange and polymer topological structure change. The structure of the unsaturated carbon-carbon triple bond that can undergo alkyne cross-metathesis reaction in the present invention is not particularly limited, and is preferably selected from the structures shown below with small steric hindrance and high reactivity:

in an embodiment of the invention, the catalyst for catalyzing alkyne cross-metathesis reactions 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 functional groups, such as catalysts 15 to 20 in the exemplified structure, etc.; catalysts are also preferably more catalytic efficient and air insensitive catalysts, such as catalysts 1, 18-20 in the example structure, etc.; the catalyst is also preferably one that can function as a catalyst at or in the range of room temperature, such as catalyst 11 in the illustrated structure. Examples of catalysts useful in the present invention for catalyzing alkyne cross-metathesis reactions include, but are not limited to, the following:

Wherein Py is ₃ Is that

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

In the embodiment of the invention, the unsaturated carbon-carbon double bond capable of generating olefin cross-metathesis and the unsaturated carbon-carbon triple bond capable of generating alkyne cross-metathesis can be a polymer precursor which is selected from the polymer precursor containing unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or can be generated or introduced on the basis of the polymer precursor without 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 severe, it is preferable to use a polymer precursor having already a carbon-carbon double bond/carbon-carbon triple bond for the reaction to achieve the purpose of introducing the carbon-carbon double bond/carbon-carbon triple bond.

Wherein the polymer precursor already contains unsaturated carbon-carbon double bonds/unsaturated carbon-carbon triple bonds, as an example, including, but not limited to, butadiene rubber, 1, 2-butadiene rubber, isoprene rubber, polynorbornene, neoprene, 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 polyesters, unsaturated polyethers and copolymers thereof, 1, 4-butylene glycol, 1, 5-bis-p-hydroxyphenyl-1, 4-pentadiene-3-one, glyceryl monoricinoleate, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloro-maleic acid, 2-methylenesuccinic acid (itaconic acid), 4' -diphenyldicarboxylic acid, 1, 5-bis-hydroxyphenyl-1, 4-pentadiene-3-one, fumaroyl chloride, 1, 4-phenylene diacryloyl chloride, citraconic anhydride, maleic anhydride, diethyl ester, monoethyl ester, fumaric acid, 2-dibromo-2, 2-fumaric acid, and the like, oligomers containing carbon-carbon double bonds/carbon-carbon triple bonds on the end group functionalized chain skeleton can also be selected.

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 dissociation, bonding and exchange reaction of bonds, thereby exhibiting dynamic reversible characteristics; 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 with each other to form a four-ring structure. The [2+2] cycloaddition dynamic covalent bond disclosed by the invention is at least one of the following structures:

wherein D is ₁ ～D ₆ Each independently selected from carbon atom, oxygen atom, sulfur atom, selenium atom, nitrogen atom, silicon atom, preferably from carbon atom, D ₁ 、D ₂ At least one of which is selected from a carbon atom or an oxygen atom or a nitrogen atom or a silicon atom; a, a ₁ ～a ₆ Respectively represent and D ₁ ～D ₆ The number of connected connections; when D is ₁ ～D ₆ A when each is independently selected from an oxygen atom, a sulfur atom, or a selenium atom ₁ ～a ₆ =0; when D is ₁ ～D ₆ Each independently selected from nitrogen atoms, a ₁ ～a ₆ =1; when D is ₁ ～D ₆ Each independently selected from carbon atoms, silicon atoms, a ₁ ～a ₆ ＝2；Q ₁ ～Q ₆ Each independently selected from carbon atoms and oxygen atoms; b ₁ ～b ₆ Respectively represent and Q ₁ ～Q ₆ The number of connected connections; when Q is ₁ ～Q ₆ B when each is independently selected from oxygen atoms ₁ ～b ₆ =0; when Q is ₁ ～Q ₆ Each independently selected from carbon atoms, b ₁ ～b ₆ ＝2；

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

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

In an embodiment of the present invention, the unsaturated double bond used to perform the [2+2] cycloaddition reaction may be selected from the group consisting of 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 for forming said [2+2] cycloaddition dynamic covalent bond, which may be selected from carbon-carbon triple bonds; wherein the unsaturated double bond, unsaturated triple bond, is preferably directly attached to an electron withdrawing or donating group, including but not limited to carbonyl, aldehyde, nitro, ester, sulfonic acid, amido, sulfone, trifluoromethyl, aryl, cyano, halogen, alkene, alkyne, and combinations thereof; the electrodonating groups include, but are not limited to, hydroxy, 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 may be formed by using unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, accumulated dienes, ketene groups themselves or unsaturated carbon-carbon triple bonds contained in the compound raw material through a [2+2] cycloaddition reaction, or may be introduced into a polymer through a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the [2+2] cycloaddition dynamic covalent bond; among them, the raw materials of the compound containing an unsaturated carbon-carbon double bond are preferably ethylene, propylene, acrolein, acrylonitrile, acrylic ester, methacrylic ester, butene dicarboxylic acid, cinnamyl alcohol, cinnamyl aldehyde, cinnamic acid, cinnamyl amide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α, β -unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butine dicarboxylic acid, azodicarboxylic acid ester, dithioester, maleimide, fullerene, derivatives of the above compounds, and the like; among them, the starting material of the compound containing a [2+2] cycloaddition dynamic covalent bond is not particularly limited, and preferably a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide and sulfur, and a mercapto compound containing a [2+2] cycloaddition dynamic covalent bond, more preferably a polyol, isocyanate, epoxy compound, alkene, alkyne containing a [2+2] cycloaddition dynamic covalent bond.

In the invention, the [4+2] cycloaddition dynamic covalent bond is formed based on [4+2] cycloaddition reaction, can be activated under certain conditions, and generates dissociation, bonding and exchange reaction of bonds, thereby exhibiting dynamic reversible characteristics; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group, 2 pi electrons are provided by a dienophile group, and a cyclic group structure is formed through addition. The [4+2] cycloaddition dynamic covalent bond disclosed by the invention is at least one of the following structures:

wherein K is ₁ 、K ₂ 、K ₅ ～K ₁₀ Each independently selected from the group consisting of carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, selenium atoms, and at K ₁ 、K ₂ Or K ₅ 、K ₆ Or K ₇ 、K ₈ Or K ₉ 、K ₁₀ At least one atom of which is selected from carbon or nitrogen or silicon; c ₁ ～c ₁₀ Respectively represent and K ₁ ～K ₁₀ The number of connected connections; when K is ₁ 、K ₂ 、K ₅ ～K ₁₀ C when each is independently selected from an oxygen atom, a sulfur atom, and a selenium atom ₁ 、c ₂ 、c ₅ ～c ₁₀ =0; when K is ₁ 、K ₂ 、K ₅ ～K ₁₀ C when each is independently selected from nitrogen atoms ₁ 、c ₂ 、c ₅ ～c ₁₀ =1; when K is ₁ 、K ₂ 、K ₅ ～K ₁₀ C when each is independently selected from carbon atoms, silicon atoms ₁ 、c ₂ 、c ₅ ～c ₁₀ ＝2；K ₃ 、K ₄ Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom; c ₃ 、c ₄ Respectively represent and K ₃ 、K ₄ The number of connected connections; when K is ₃ 、K ₄ C when each is independently selected from oxygen atom, sulfur atom ₃ 、c ₄ =0; when K is ₃ 、K ₄ C when each is independently selected from nitrogen atoms ₃ 、c ₄ ＝1；I ₁ 、I ₂ Each 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 molecule hydrocarbon group, more preferably selected 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, a secondary amine groupSubstituted forms, amide groups, ester groups;

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

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be bound to form rings, to different atoms

May also 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 include: />

Wherein, the [4+2] cycloaddition dynamic covalent bond can be connected with the light-control locking element to form a light-control DA structure. The light-operated locking element can react with a dynamic covalent bond and/or the light-operated locking element under specific illumination conditions to change the dynamic covalent bond structure, thereby achieving the purpose of locking/unlocking DA reaction; wherein, when the dynamic covalent bond is locked, it cannot or is more difficult to perform DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it can perform DA equilibrium reaction, realizing dynamic characteristics.

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

wherein, the liquid crystal display device comprises a liquid crystal display device,

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

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

the [4+2] cycloaddition dynamic covalent bond with the light control function, which is connected with the light control locking element, is preferably selected from at least one of the following general structures:

wherein K is ₁ 、K ₂ 、K ₃ 、K ₄ 、K ₅ 、K ₆ Each independently selected from carbon, oxygen, sulfur, nitrogen, and at K ₁ 、K ₂ Or K ₃ 、K ₄ Or K ₅ 、K ₆ At least one of which is selected from carbon atoms; a, a ₁ 、a ₂ 、a ₃ 、a ₄ 、a ₅ 、a ₆ Respectively represent and K ₁ 、K ₂ 、K ₃ 、K ₄ 、K ₅ 、K ₆ The number of connected connections; when K is ₁ 、K ₂ 、K ₃ 、K ₄ 、K ₅ 、K ₆ A when each is independently selected from an oxygen atom and a sulfur atom ₁ 、a ₂ 、a ₃ 、a ₄ 、a ₅ 、a ₆ =0; when K is ₁ 、K ₂ 、K ₃ 、K ₄ 、K ₅ 、K ₆ Each independently selected from nitrogen atoms, a ₁ 、a ₂ 、a ₃ 、a ₄ 、a ₅ 、a ₆ =1; when K is ₁ 、K ₂ 、K ₃ 、K ₄ 、K ₅ 、K ₆ Each independently selected from carbon atoms, a ₁ 、a ₂ 、a ₃ 、a ₄ 、a ₅ 、a ₆ ＝2；I ₁ 、I ₂ 、I ₃ Each 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 ₁ 、I ₂ 、I ₃ Each independently absent, b=2; when I ₁ 、I ₂ 、I ₃ B=1 when each is independently selected from the group consisting of oxygen atoms, 1 '-carbonyl groups, methylene groups and substituted forms thereof, 1, 2-ethylene groups and substituted forms thereof, 1' -vinyl groups and substituted forms thereof; m is selected from oxygen atom, nitrogen atom and bivalent alkoxy chain

n=2, 3, 4), preferably an oxygen atom, 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; c (C) ₁ 、C ₂ 、C ₃ 、C ₄ 、C ₅ 、C ₆ Representing carbon atoms in different positions; different +.>

Can be linked to form a ring, +. >

May also be linked in a ring, where, preferably, at K ₁ And K is equal to ₂ Between, K ₃ And K is equal to ₄ Between, K ₅ And K is equal to ₆ Between C ₁ And C ₂ Between C ₃ And C ₄ Between C ₅ And C ₆ Forming a ring between the two rings; the rings formed may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof, and the ring-forming atoms may be 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 or may not be substituted with any substituent; wherein K is ₁ And K is equal to ₂ Between, K ₃ And K is equal to ₄ Between, K ₅ And K is equal to ₆ The ring formed therebetween is preferably of the structure:

C ₁ and C ₂ Between C ₃ And C ₄ The ring formed therebetween is preferably of the structure:

/>

C ₅ and C ₆ The ring formed therebetween is preferably of the structure:

in an embodiment of the present invention, the dienyl group used for performing the [4+2] cycloaddition reaction may be any suitable group containing conjugated diolefins and derivatives thereof, for example butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives thereof, and the like; a dienophile group for forming said [4+2] cycloaddition dynamic covalent bond, which contains any suitable unsaturated double bond or unsaturated triple bond, such as a carbon-carbon double bond, carbon-carbon triple bond, carbon-oxygen double bond, carbon-sulfur double bond, carbon-nitrogen double bond, nitrogen-nitrogen double bond, etc.; wherein the diene group, unsaturated double bond or unsaturated triple bond in the dienophile group, is preferably directly attached to an electron withdrawing or donating group, including but not limited to carbonyl, aldehyde, nitro, ester, sulfonic, amido, sulfone, trifluoromethyl, aryl, cyano, halogen, alkene, alkyne, and combinations thereof; the electrodonating groups include, but are not limited to, hydroxy, 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 may be formed by a [4+2] cycloaddition reaction between a compound raw material containing a dienoic group and a compound raw material containing a dienophile group, or may be introduced into a polymer by a 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, derivatives of the above compounds and the like; wherein the raw material of the compound containing dienophile group can be selected from ethylene, propylene, acrolein, acrylonitrile, acrylic ester, methacrylic ester, butene dicarboxylic acid, cinnamyl alcohol, cinnamyl aldehyde, cinnamic acid, cinnamyl amide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, alpha, beta-unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butine dicarboxylic acid, azodicarboxylic ester, dithioester, maleimide, fullerene, derivatives of the above compounds, and the like; among them, the starting material of the compound containing a [4+2] cycloaddition dynamic covalent bond is not particularly limited, and preferably a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide and sulfur, and a mercapto compound containing a [4+2] cycloaddition dynamic covalent bond, more preferably a polyol, isocyanate, epoxy compound, alkene, alkyne containing a [4+2] cycloaddition dynamic covalent bond.

In the invention, the [4+4] cycloaddition dynamic covalent bond is formed based on [4+4] cycloaddition reaction, can be activated under certain conditions, and generates dissociation, bonding and exchange reaction of bonds, thereby exhibiting dynamic reversible characteristics; wherein, the [4+4] cycloaddition reaction refers to a reaction that two conjugated diene groups respectively provide 4 pi electrons and form a cyclic group structure through addition. The [4+4] cycloaddition dynamic covalent bond disclosed by the invention is selected from the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

the cyclic group structure represented is an aromatic ring or a hybrid aromatic ring, the ring-forming atoms of the cyclic group structure are each independently selected from a carbon atom, a nitrogen atom or other hetero atoms, and the cyclic group structure is preferably selected from a 6-to 50-membered ring, more preferably from a 6-to 12-membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the cyclic group structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, an azabenzene, an azanaphthalene, an azaanthracene, or a substituted form of the above groups; i ₆ ～I ₁₄ Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imide group, and a divalent small molecule hydrocarbon group, more preferably selected from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, an amide group, an ester group, and an imide group; / >

Represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; different +.>

Can be linked to form a ring, +.>

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

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

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

In an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond and [4+4] cycloaddition dynamic covalent bond includes but is not limited to temperature regulation, adding catalyst, irradiation, radiation, microwave and other action modes. For example, dissociation can occur by heating the [2+2] cycloaddition dynamic covalent bond 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 undergo [4+2] cycloaddition reaction to form a dynamic covalent bond at room temperature or under heating, the formed dynamic covalent bond can be dissociated at the temperature higher than 110 ℃, and then the dynamic covalent bond can be formed again through cooling. For another example, the [2+2] cycloaddition dynamic covalent bond can be formed by [2+2] cycloaddition reaction under the condition of long wavelength light irradiation, and then the dissociation of the dynamic covalent bond is generated under the condition of short wavelength light irradiation, so as to obtain the unsaturated carbon-carbon double bond; for example, the cinnamoyl unsaturated carbon-carbon double bond can be subjected to [2+2] cycloaddition reaction under the ultraviolet irradiation condition that lambda is more than 280nm to form a dynamic covalent bond, and the bond is dissociated under the ultraviolet irradiation condition that lambda is less than 280nm to obtain the cinnamoyl unsaturated carbon-carbon double bond; the unsaturated carbon-carbon double bond of coumarin can be subjected to [2+2] cycloaddition reaction to form dynamic covalent bond under the ultraviolet irradiation condition that lambda is more than 319nm, and the bond is dissociated under the ultraviolet irradiation condition that lambda is less than 319nm, so that the unsaturated carbon-carbon double bond of coumarin is obtained again. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction under ultraviolet light irradiation at λ=250 nm to form a dynamic covalent bond. For another example, anthracene may undergo a [4+4] cycloaddition reaction to form a dynamic covalent bond under ultraviolet light irradiation conditions of λ=365 nm, and then undergo bond dissociation under ultraviolet light irradiation conditions of λ less than 300 nm. In addition, the [2+2], [4+2], [4+4] cycloaddition reaction can be performed under the catalysis 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, trifluoromethane sulfonate, alkyl metal compound, borane, boron trifluoride and its derivatives, aryl boron difluoride, scandium trifluoroalkyl sulfonate, etc., preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethyl aluminum dichloride, ferric tribromide, ferric trichloride, tin tetrachloride, borane, boron trifluoride diethyl ether complex, scandium trifluoromethane sulfonate; such lewis bases include, but are not limited to, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), azacyclo-carbene (NHC), quinidine, quinine, and the like; examples of the metal catalyst used for catalyzing [2+2], [4+2], [4+4] cycloaddition reaction in the present invention include, but are not limited to, the following:

In the invention, the mercapto-Michael addition dynamic covalent bond can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond occur, so that the dynamic reversible characteristic is shown; the sulfhydryl-Michael addition dynamic covalent bond disclosed by the invention is at least one of the following structures:

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

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein the differences on the same carbon atom are +.>

Can be linked to form a ring, +.>

Or may be linked to form a ring, carbon atom and +.>

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

In an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of the thiol-michael addition dynamic covalent bond includes, but is not limited to, temperature adjustment, catalyst addition, pH adjustment, and the like. For example, dissociated thiol-Michael addition dynamic covalent bonds can be regenerated by heating or exchanged for dynamic covalent bonds, so that the polymer can achieve self-healing and reworkability. For another example, for thiol-Michael addition dynamic covalent bonds, neutral or weakly basic solutions may be selected to dissociate and thus be in dynamic reversible equilibrium. For another example, the presence of a catalyst can promote the formation and exchange of dynamic covalent bonds, and the thiol-Michael addition reaction catalyst includes, but is not limited to, lewis acids, organic phosphides, organic base catalysts, nucleophilic catalysts, ionic liquid catalysts, and the like; such Lewis acids, including but not limited to, metal chlorides, metal iodides, triflates, metal alkyls, boranes, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkyl sulfonates, and the like; the organic phosphide comprises, but is not limited to, potassium phosphate, tri-n-propyl phosphine, dimethyl phenyl phosphine, methyl diphenyl phosphine and triphenyl phosphine; organic base catalysts including, but not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, and the like; the nucleophilic catalyst comprises, but is not limited to, 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, 0] dec-5-ene, 1, 4-diazabicyclo [2, 2] octane, imidazole, 1-methylimidazole; the ionic liquid catalyst comprises, but is not limited to, 1-butyl-3-methylimidazole hexafluorophosphate, 1- (4-sulfonic group) butylpyridine, 1-butyl-3-methylimidazoline tetrahydroboric acid, 1-allyl-3-methylimidazole chloride and the like.

In the embodiment of the present invention, the thiol-michael addition dynamic covalent bond may be formed by using a thiol group contained in a compound raw material and conjugated olefin or conjugated alkyne through a thiol-michael addition reaction, or may be introduced into a polymer through a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a thiol-michael addition dynamic covalent bond. Wherein the raw material of the compound containing conjugated olefin or conjugated alkyne can be selected from acrolein, acrylic acid ester, propiolate, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, butenoate, butenodiate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives of the above compounds; among them, the starting materials for the compound containing a thiol-michael addition dynamic covalent bond are not particularly limited, and preferably polyols, isocyanates, epoxy compounds, olefins, alkynes, carboxylic acids, esters, and amides containing a thiol-michael addition dynamic covalent bond, and more preferably polyols, isocyanates, epoxy compounds, olefins, and alkynes containing a thiol-michael addition dynamic covalent bond.

In the invention, the amine alkene-Michael addition dynamic covalent bond can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond occur, so that the dynamic reversible characteristic is shown; the amine alkene-Michael addition dynamic covalent bond described in the present invention is selected from the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

In an embodiment of the present invention, the "certain condition" for activating dynamic reversibility of an amine alkene-michael addition dynamic covalent bond includes, but is not limited to, modes of action such as temperature adjustment, pH adjustment, and the like. For example, for amine alkene-Michael addition dynamic covalent bonds, a solution with weak acidity (pH 5.3) can be selected to dissociate and thus be in dynamic reversible equilibrium. For another example, dissociated amine alkene-Michael addition dynamic covalent bonds can be regenerated by heating at 50-100deg.C to form the dynamic covalent bonds or exchange of dynamic covalent bonds, such that the polymer can be self-healing and reworkability.

In the embodiment of the invention, the amine alkene-Michael addition dynamic covalent bond can be formed by taking terephthalaldehyde, malonic acid and malonic acid diester as raw materials to prepare an intermediate product and then reacting the intermediate product with an amino compound through amine alkene-Michael addition reaction.

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

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

In embodiments of the invention, the "conditions" for activating dynamic reversibility of the triazolinedione-indole-based dynamic covalent bond include, but are not limited to, modes of action such as temperature regulation, pressurization, addition of a catalyst, and the like. For example, the indole and the diazolidinedione can generate a dynamic covalent bond based on the triazolinedione-indole at the temperature of 0 ℃, then the bond is dissociated by heating, and then the dynamic covalent bond is regenerated by cooling or the dynamic covalent bond is exchanged, so that the polymer can obtain self-repairing property and reworkability. For another example, for a dynamic covalent bond based on a triazolinedione-indole, a neutral or weakly basic solution may be chosen to cause dissociation and thus be in dynamic reversible equilibrium. For 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 acids include, but are not limited to, metal chlorides, metal iodides, triflates, metal alkyls, boranes, boron trifluoride and its derivatives, arylboron difluorides, scandium trifluoroalkyl sulfonates, and the like.

In the embodiment of the invention, the dynamic covalent bond based on triazolinedione-indole can be formed by using the addition reaction of the oxadiazolinedione group and the derivative thereof contained in the compound raw material and indole and the derivative thereof through an Alder-olefin. Wherein the indole and its derivative raw materials may be 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-ethynylindole, 5-amino-2-phenylindole, 2-phenyl-1H-indol-6 amine, 2-phenyl-1H-indole-3-acetaldehyde, (2-phenyl-1H-indole-3-alkyl) carboxylic acid, 6-amino-2-phenyl-1H-indole-3-carboxylic acid ethyl ester, 2- (2-aminophenyl) indole, 2-phenylindole-3-acetonitrile, 4, 6-diamidino-2-phenylindole and the like.

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

Wherein, the liquid crystal display device comprises a liquid crystal display device,

represents a linkage to a polymer chain, a crosslinked network chain, or any other suitable group/atom; wherein +.>

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

Wherein Me represents methyl, et represents ethyl, nBu represents n-butyl, ph represents phenyl, and Mes represents trimethylphenyl.

In embodiments of the invention, the "certain conditions" for activating dynamic reversibility of the dynamic covalent bond based on the diazacarbene include, but are not limited to, modes of action such as temperature regulation, addition of solvents, and the like. For example, the self-repairability and reworkability of the polymer may be achieved by heating the diazacarbene-based dynamic covalent bond at a temperature above 90 ℃ to dissociate it into the diazacarbene structure, and then regenerating the dynamic covalent bond by cooling or performing an exchange of the dynamic covalent bond.

In an embodiment of the present invention, the diazacarbene-based dynamic covalent bond may be formed by using the diazacarbene group contained in the compound starting material itself or by reacting it with thiocyanogen.

In the invention, the benzoyl-based dynamic covalent bond can be activated under certain conditions to break to form free radicals, and the free radicals can be reversibly coupled or exchanged to reform the dynamic covalent bond to show dynamic reversible characteristics. 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;

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

In an embodiment of the present invention, the "certain conditions" for activating the benzoyl-based dynamic reversibility of the dynamic covalent bond include, but are not limited to, modes of action such as temperature regulation, light irradiation, radiation, microwaves, and the like. For example, the dynamic covalent bond can be broken to form free radicals by heating, so that dissociation and exchange reaction of the dynamic covalent bond occur, and the dynamic covalent bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairing property and reworkability. The dynamic covalent bond can be broken by light to form free radicals, so that dissociation and exchange reaction of the dynamic covalent bond occur, and the dynamic covalent bond is reformed after the light is removed, so that the polymer can obtain self-repairing property and reworkability. Radiation, microwaves can generate free radicals in the system to react with dynamic covalent bonds to obtain self-repairability and reworkability.

In the invention, the hexahydrotriazine dynamic covalent bond can be activated under a certain condition, and generates dissociation, bonding and exchange reaction of the bond, thereby exhibiting dynamic reversible characteristics; wherein, the "certain condition" for activating dynamic reversibility of hexahydrotriazine dynamic covalent bond refers to proper pH condition, heating condition and the like. The hexahydrotriazine dynamic covalent bond disclosed by the invention is at least one selected from the following structures:

wherein, the liquid crystal display device comprises a liquid crystal display device,

representing a chain linked to a polymer, a crosslinked network orAny other suitable group/atom linkage. Typical hexahydrotriazine dynamic covalent bond structures can be exemplified by: />

In an embodiment of the present invention, the suitable pH condition for performing the dynamic reversible reaction of the hexahydrotriazine dynamic covalent bond refers to swelling the dynamic polymer in a solution with a certain pH value or wetting the surface thereof with a solution with a certain pH value, so that the hexahydrotriazine dynamic covalent bond in the dynamic polymer exhibits dynamic reversibility. For example, hexahydrotriazines dynamic covalent bonds can be dissociated at a pH < 2 and reformed at neutral pH, so that the polymer can be self-repairing and reworkable. Wherein, the acid-base reagent for adjusting the pH can be selected from: (1) inorganic acid, organic acid and acid salt catalyst. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; the organic acid may be exemplified by methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; salts such as sulfate, bisulfate, hydrogen phosphate and the like can be exemplified. (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, brilliant carbonate, and potassium t-butoxide. (3) Examples of the group IIA alkali metal and its compound include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Examples of the aluminum metal and the compound thereof include aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrous aluminum oxide and sodium hydroxide, an aluminum alkoxide compound, and the like. (5) Organic compounds such as ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldoxime, hydrazine monohydrate, N' -diphenylthiourea, scandium triflate (Sc (OTf) ₃ ) Etc. (6) Examples of the divalent copper compound include copper acetate. (7) Ferric iron compounds, canExamples thereof include an aqueous solution of ferric trichloride, ferric sulfate hydrate, ferric nitrate hydrate, and the like. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, copper acetate, and potassium t-butoxide are preferable.

In the embodiment of the invention, the hexahydrotriazine dynamic covalent bond can be formed by utilizing amino groups and aldehyde groups contained in compound raw materials to form (I) hexahydrotriazine dynamic covalent bonds through polycondensation reaction under low temperature conditions (such as 50 ℃), and then (II) hexahydrotriazine dynamic covalent bonds are formed by heating under high temperature conditions (such as 200 ℃); the compound starting materials containing dynamic covalent bonds of hexahydrotriazines can also be used to introduce polymers by polymerization/crosslinking reactions between the reactive groups they contain. Among them, the raw materials of the compound containing a dynamic covalent bond of hexahydrotriazine is not particularly limited, and preferably polyols, isocyanates, epoxy compounds, alkene, alkyne, carboxylic acid, ester, amide containing a dynamic covalent bond of hexahydrotriazine, more preferably polyols, isocyanates, epoxy compounds, alkene, alkyne containing a dynamic covalent bond of hexahydrotriazine.

In the invention, the dynamically exchangeable trialkylsulfonium bond can be activated under the heating condition and generates alkyl exchange reaction to show dynamic reversible property; wherein the term "transalkylation" refers to the formation of new trialkylsulfonium bonds elsewhere accompanied by the dissociation of old trialkylsulfonium bonds, resulting in chain exchange and a change in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under heating at 130 to 160 ℃. The dynamically exchangeable trialkylsulfonium bonds described in the present invention are selected from the following structures:

wherein X is ^- Selected from sulfonates, preferably benzenesulfonate, more preferably p-bromobenzenesulfonate;

representing a chain of polymers, crosslinked network orAny other suitable group/atom linkage.

In an embodiment of the present invention, the dynamically exchangeable trialkylsulfonium bond may be formed by a thiol-michael addition reaction of a thiol 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 at least one selected from the following structures:

wherein X is selected from a carbon atom or a 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 crosslinked network chain, or any other suitable group/atom; wherein a represents the number of connections to Y; when Y is selected from an aluminum atom, a chromium atom, a phosphorus atom, a=2; when Y is selected from titanium atom, tin atom, zirconium atom, a=3; different +.>

Can be linked to form a ring, +.>

May also 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 or a dynamic phosphite bond. Typical examples of the dynamic acid ester bond structure include:

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

In the invention, the diketene enamine dynamic covalent bond can be activated under a certain condition, and generates dissociation, bonding and exchange reaction of the bond, thereby exhibiting dynamic reversible characteristics; the diketene enamine dynamic covalent bond described in the present invention is selected from the following structures:

/>

Wherein, the liquid crystal display device comprises a liquid crystal display device,

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

In embodiments of the present invention, the "certain conditions" for activating dynamic reversibility of the diketene enamine dynamic covalent bond include, but are not limited to, heating, suitable acidic aqueous conditions, etc., such that the polymer exhibits good self-healing, recycling recyclability, stimulus responsiveness, etc. In the embodiment of the invention, the diketene enamine dynamic covalent bond can be dissociated in a strong acid aqueous solution, is formed under anhydrous neutral condition, has good pH stimulus response, and can obtain dynamic reversibility through adjustment of an acidic environment. In embodiments of the present invention, acids that may be used to provide dynamic reactions include, but are not limited to, permanganate, hydrochloric acid (hydrochloric acid), sulfuric acid, nitric acid, perchloric acid, selenoic 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 an acid vapor, without limitation.

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

The boron-free dynamic covalent bond contained in the polymer can be kept stable under specific conditions, the purpose of providing a balance structure and mechanical strength is achieved, and dynamic reversibility can be shown under other specific conditions, so that the material can be completely self-repaired, recycled and plastically deformed; meanwhile, the existence of different types of boron-free dynamic covalent bonds enables the polymer to show different response effects to external stimuli such as heat, light, pressure, pH, redox and the like, and the dynamic reversible balance can be promoted or slowed down under proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.

In order to achieve dynamic reversible balance of the boron-free dynamic covalent bond, thereby having dynamic reversibility and showing good dynamic reversibility effect, the boron-free dynamic covalent bond is required to have dynamic reversibility by means of temperature adjustment, redox agent addition, catalyst addition, illumination, radiation, microwave, plasma action, pH adjustment and the like. Among them, the temperature regulation modes that can be used in the present invention include, but are not limited to, water bath heating, oil bath heating, electric heating, microwave heating, laser heating, etc. The type of illumination used in the present invention is not limited, and Ultraviolet (UV), infrared, visible, laser, and chemical fluorescence are preferable, and ultraviolet, infrared, and visible are more preferable. The radiation employed in the present invention includes, but is not limited to, high energy ionizing radiation such as alpha rays, beta rays, gamma rays, x rays, electron beams, and the like. The plasma action used in the present invention means catalytic action by an ionized gaseous substance composed of positive and negative ions generated by ionization of atoms and radicals of which some electrons are deprived. The microwaves used in the present invention refer to electromagnetic waves having a frequency of 300MHz to 300 GHz.

In the invention, dynamic covalent crosslinking is used as a covalent crosslinking structure, so that good stability can be provided, and the effects of stabilizing the balance structure and providing good mechanical strength can be achieved; the polymer material can show dynamic covalent property and dynamic reversibility under specific conditions, so that molecular-level and microscopic self-repairing performance can be realized through dynamic reversibility of dynamic covalent crosslinking when local structural damage occurs to the polymer material. Different kinds of dynamic covalent bonds are introduced into the polymer, so that the polymer can show different response effects to external stimuli such as heat, illumination, pH, redox agents and the like, and the dynamic reversible balance can be promoted or slowed down under proper environment by selectively controlling the external conditions, so that the polymer is in a required state. The dynamic covalent bond, especially the weak dynamic covalent bond, can also be used as a sacrificial bond to absorb impact energy and improve toughness and damage resistance; the strong dynamic covalent bond can also be the dynamic dilatant of the polymer and improve the tear resistance of the material.

In the present invention, the non-covalent interactions include supramolecular interactions, phase separation and crystallization; the supermolecular interactions include hydrogen bonding interactions and non-hydrogen bonding supermolecular interactions, wherein the non-hydrogen bonding supermolecular interactions include, but are not limited to, at least one of the following: metal-ligand action, ion cluster action, ion-dipole action, host-guest action, metallophilic action, dipole-dipole action, halogen bond action, lewis acid base pair action, cation-pi action, anion-pi action, benzene-fluorobenzene action, pi-pi stacking action, ion hydrogen bonding action, free radical cation dimerization action.

In the present invention, the non-covalent effect may be a weak dynamic non-covalent effect/supramolecular effect that does not undergo dissociation/cleavage during normal use of the polymer, which generally cannot undergo dynamic dissociation and generate interconverted dynamic behavior at the material working temperature without applying external field effects or the like; non-covalent/supramolecular interactions with strong dynamics during normal use of the polymer, which typically can occur dynamic dissociation and generation of interconverted dynamic behavior at material operating temperatures without application of external fields or the like; the material operating temperature is generally not higher than 60 ℃, preferably not higher than 25 ℃.

In the present invention, the hydrogen bonding refers to any suitable supermolecular bonding established by hydrogen bonding, which generally generates a hydrogen bonding linkage in the form of Z-H … Y by using hydrogen as a medium between Z and Y through a hydrogen atom covalently connected with an atom Z with high electronegativity and an atom Y with high electronegativity and a small radius, wherein Z, Y is any suitable atom with high electronegativity and a small radius, which may be the same element or different element, and may be selected from F, N, O, C, S, cl, P, br, I and other atoms, more preferably from F, N, O atoms, and still more preferably from O, N atoms. Wherein the hydrogen bond may exist as a supramolecular polymerization and/or cross-linking and/or intra-chain cyclization, i.e., the hydrogen bond may serve only to connect two or more segment units to increase the polymer chain size but not to crosslink the supramolecules, or the hydrogen bond may serve only to crosslink the interchain supramolecules, or to ring only in-chain, or a combination of any two or more of the three.

In embodiments of the present invention, the hydrogen bond may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by the donor (H, i.e., a hydrogen atom) and the acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of the hydrogen bond group, and each H … Y is combined into one tooth. The hydrogen bond formation conditions of hydrogen bond groups with one tooth, two teeth, three teeth, four teeth and more than four teeth are respectively and schematically illustrated.

The bonding of hydrogen bonds of one, two, three, four or more teeth can be specifically exemplified as follows (but the invention is not limited thereto):

in the embodiment of the invention, the more the number of teeth of the hydrogen bond is, the larger the synergistic effect is, the larger the strength of the hydrogen bond is, and the weaker the dynamic property of the hydrogen bond is. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond action is weak, and the effects of promoting the polymer to keep a balance structure and improving the mechanical properties (modulus and strength) can be achieved. If the number of teeth of the hydrogen bond is small, the strength is low, and the dynamics of the hydrogen bond action is strong.

In a preferred embodiment of the invention, the polymer only contains one-tooth hydrogen bond and/or two-tooth hydrogen bond, and the hydrogen bond has low action strength and strong dynamic property, is beneficial to inhibiting the low-temperature hardening process of the slow rebound polymer and improves the slow rebound performance at low temperature.

In another preferred embodiment of the present invention, the polymer only contains hydrogen bonds with three teeth or more, and the strength of the hydrogen bond is high, which is favorable for improving the mechanical strength and modulus of the material and improving the tear resistance of the material.

In embodiments of the invention, the hydrogen bond may be created by non-covalent interactions that exist between any suitable hydrogen bonding groups. Wherein the hydrogen bond group may contain only a hydrogen bond donor, or only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.

The hydrogen bond donor described in the present invention may be any suitable donor group containing a hydrogen atom, preferably containing at least one of the following structural components:

more preferably, at least one of the following structural components is contained:

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

The hydrogen bond acceptor described in the present invention may be an acceptor group containing any suitable electronegative atom (e.g., O, N, S, F, etc.), preferably containing at least one of the following structural components:

wherein A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atoms and monosubstituted alkyl; x is selected from halogen atoms;

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

The hydrogen bond group containing both a hydrogen bond donor and a hydrogen bond acceptor in the present invention may be any suitable hydrogen bond group containing a hydrogen bond donor and a hydrogen bond acceptor, and preferably contains at least one of the following structural components:

it is further preferable to contain at least one of the following structural components:

wherein, the liquid crystal display device comprises a liquid crystal display device,

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

In the present invention, the hydrogen bond groups may be present only on the polymer chain backbone (including the main chain and the side chain/branched/forked chain backbone), referred to as backbone hydrogen bond groups, wherein at least part of the atoms are part of the chain backbone; may also be present only on side groups of the polymer chain backbone (including both main and side/branched/forked chain backbones), referred to as side group hydrogen bonding groups, which may also be present on the multi-stage structure of the side groups; or may be present only on the end groups of the polymer chain backbone/small molecule, known as end hydrogen bonding groups; or at least two of the polymer chain skeleton, the side group and the end group; the hydrogen bonding groups may also be present in polymer constituents such as small molecule compounds or fillers, known as other hydrogen bonding groups. When hydrogen bond groups are present on at least two of the polymer chain backbone, side groups, and end groups simultaneously, hydrogen bonds may be formed between the hydrogen bond groups in different positions in certain circumstances, for example, the backbone hydrogen bond groups may form hydrogen bonds with the side group hydrogen bond groups.

As examples, the following skeletal hydrogen bond groups may be mentioned, but the present invention is not limited thereto:

as examples, the following side hydrogen bond groups/end hydrogen bond groups may be mentioned, but the present invention is not limited thereto:

/>

wherein x, m, n are the number of repeating units, which may be a fixed value or an average value, preferably less than 20, more preferably less than 5.

Other hydrogen bonding groups in the present invention may be any suitable hydrogen bonding structure.

The types of hydrogen bonding in the present invention are varied and include, but are not limited to, hydrogen bonding of one or more of skeletal hydrogen bonding groups, side group hydrogen bonding groups, end group hydrogen bonding groups, or other hydrogen bonding groups, and thereby achieve a wide range of adjustable hydrogen bonding/crosslinking of supermolecular strength, supermolecular dynamics, and supermolecular crosslink density. The different hydrogen bond effects have respective structural differences and performance characteristics, such as the hydrogen bond effects formed by participation of the side group hydrogen bond groups and the end group hydrogen bond groups, and have the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of the hydrogen bond density, and the like, so that a quick self-repairing process is easy to obtain, and the tear resistance can be better improved; the skeleton hydrogen bond group is positioned on the skeleton chain, so that the mechanical strength and the structural stability are easier to improve, a high-strength polymer material is convenient to obtain, and other hydrogen bond groups can further enrich the hydrogen bond action form.

In the present invention, one or more hydrogen bonding groups may be contained in the same polymer system, or one or more hydrogen bonding groups may be contained in the same crosslinked network, that is, one or more combinations of hydrogen bonding groups may be contained in the polymer. The hydrogen bonding groups may be formed by reaction between any suitable groups, for example: formed by covalent reactions between carboxyl groups, acyl halide groups, anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reactions between succinimide groups and amino, hydroxyl, sulfhydryl groups.

In the present invention, the metal-ligand interaction refers to a supermolecular interaction established by a coordination bond formed by a ligand group (represented by L) and a metal center (represented by M). The ligand group is selected from cyclopentadiene, or a structural unit containing at least one coordination atom or ion (represented by A). The metal center can be selected from metal ions, metal centers of metal chelates, metal centers of metal organic compounds and metal centers of metal inorganic compounds. Wherein one coordination atom or ion may form one or more coordination bonds with one or more metal centers, and one metal center may also form one or more coordination bonds with one or more coordination atoms or ions. The number of coordination bonds formed by one ligand group and the metal center is referred to as the number of teeth of the ligand group. In the embodiment of the present invention, in the same system, one metal center can form a metal-ligand effect with one or more ligands of a monodentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can be connected into a ring through the metal center, so that the present invention can effectively provide a dynamic metal-ligand effect with sufficiently abundant types, amounts and performances, and the following structures shown in the general formula are given as examples, but the present invention is not limited thereto:

Wherein A is a coordinating atom or ion, M is a metal center, and each ligand group forms a A-M bond with the same metal center to form a tooth, wherein, a single bond is used for connecting A to represent that the coordinating atom or ion belongs to the same ligand group, when one ligand group contains two or more coordinating atoms or ions, A can be the same atom or different atoms and is selected from boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferred is nitrogen. In some cases, a exists as a negative ion;

is a cyclopentadiene ligand. In the present invention, it is preferable that one coordinating atom or ion forms one coordination bond with only one metal center, and therefore the number of coordinating atoms or ions contained in the ligand group is the number of teeth of the ligand group. The ligand group reacts with the metal-ligand formed by the metal center (in M-L _x X represents the number of ligand groups that interact with the same metal center) is related to the type and number of coordinating atoms or ions on the ligand groups, the type of metal center, the valence state and ion, etc.

In an embodiment of the invention, when forming supramolecular-acting crosslinks above the gel point, one metal center is capable of forming a metal-ligand interaction with at least two of the ligand groups (i.e., M-L ₂ Structure) or a metal-containing structure formed by a plurality of ligands and the same metal centerLigand action, wherein two or more ligand groups may be the same or different. The coordination number of one metal center is limited, the more coordination atoms or ions of the ligand groups, the fewer the number of ligands that one metal center can coordinate, the lower the degree of supermolecular cross-linking based on metal-ligand interaction; however, the more the number of teeth formed by each ligand to the metal center, the more dynamic the ligand, and therefore, the more tridentate ligand groups are preferred in the present invention.

In embodiments of the invention, there may be only one ligand in one polymer chain or one polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure, and a framework ligand, a side group ligand and a terminal group ligand can have the same core ligand structure, and the difference is that the connection points and/or positions of the core ligand structure to a polymer chain or a small molecule are different. Suitable ligand combinations can be effective in preparing polymers with specific properties, for example, to achieve synergistic and/or orthogonal effects, enhancing the overall properties of the material. Suitable ligand groups (core ligand structures) can be exemplified as follows, but the invention is not limited thereto:

One example of a dentate ligand group is as follows:

the bidentate ligand groups are exemplified as follows:

the tridentate ligand group is exemplified as follows:

the tetradentate ligand groups are exemplified as follows:

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the multidentate ligands are for example as follows:

in embodiments of the present invention, the metal center M may be any suitable metal ion or metal center of a 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.

The metals involved are preferably metals of the first to seventh sub-groups and the eighth sub-group. The metals of the first to seventh sub-groups and eighth sub-groups also include lanthanide metals (i.e. La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu) and actinide metals (i.e. Ac, th, pa, U, np, pu, am, cm, bk, cf, es, fm, md, no, lr).

The metals involved are more preferably metals of the first subgroup (Cu, ag, au), metals of the second subgroup (Zn, cd), metals of the eighth subgroup (Fe, ru, os, co, rh, ir, ni, pd, pt), metals of the lanthanide series (La, eu, tb, ho, tm, lu), metals of the actinide series (Th). Further preferably Cu, zn, fe, co, ni, pd, ag, pt, au, la, ce, eu, tb, th, to obtain a stronger dynamic.

In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples may be, for example, as follows:

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 may be incorporated into the polymer chain at the appropriate position by means of suitable covalent chemical linkages. Those skilled in the art may implement the logic and context of the present invention reasonably efficiently.

In the embodiment of the present invention, the metal inorganic compound is preferably oxide or sulfide particles of the above metal, particularly nanoparticles.

In an embodiment of the present invention, a chelate compound in which a metal chelate compound of a suitable metal center preferably has a gap of a coordination site, or a chelate compound in which a part of a ligand may be substituted with the framework ligand of the present invention may be provided.

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 action with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

In the present invention, the ionic action refers to a supermolecular action formed by a coulomb force between a positive ionic group and a negative ionic group, wherein the polymer structure contains at least one pair of positively and negatively charged ionic groups. The positive ion group refers to a group having a positive charge, and examples thereof include:

preferably->

The negative ion group refers to a group having negative charge, and examples thereof include:

preferably->

Wherein the anionic groups may also be present in clay minerals including, but not limited to, kaolinite, antigorite, pyrophyllite, talc, montmorillonite, saponite, magadiite, hydromica, mica, chlorite, palygorskite, sepiolite. In the case of a special case,the positive and negative ionic groups can be in the same compound structure, such as choline glycerophosphate, 2-methacryloxyethyl phosphorylcholine, l-carnitine, methacryloxyethyl sulfobetaine, and the like. The ionic effect can exist in the polymer stably, and the strength of the ionic effect can be controlled well by changing the concentration and the kind of the ionic group.

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

and inorganic clay (nano) particles with anions.

In the embodiment of the invention, the ion cluster effect is formed by aggregation of tens to tens of anion-cation pairs. Wherein the anionic group is an organic group which is easier to lose proton, and the cationic group is an organic group which is easier to accept proton or a metal ion which is easier to lose electron. As examples, 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 an anion-cation pair 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 an anion-cation pair 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 ion is not directly connected with the polymer, so that the strength of the ion cluster effect can be regulated by changing the number and the type of the counter ion.

In an embodiment of the present invention, the position of the cation and anion in the polymer molecule is not limited when the ion cluster is present.

In the embodiment of the present invention, the anion and cation pair capable of forming ion clusters is not particularly limited, and some suitable anion and cation pairs can be exemplified as follows, but the present invention is not limited thereto:

in the present invention, the ion-dipole action refers to the supermolecule action formed by the interaction of an electric dipole generated by the asymmetric distribution of electrons caused by the uneven charge distribution due to the induction of atoms with larger electronegativity when two atoms with different electronegativity form a bond. The ionic group may be any suitable charged group, for example, but the invention is not limited thereto:

preferably->

The electric dipole may be generated by bonding any suitable two atoms having different electronegativity, for example, 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-I, H-O, H-S, H-N, preferably c≡ N, C = O, C-F, H-O. The ion-dipole effect can exist stably in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of acting force generation and dissociation are mild.

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:

in the present invention, the host-guest interaction refers to any suitable supermolecular interaction host established by the host-guest interaction. Wherein the main body (represented by H) is a compound (macromolecular or inorganic organic ion skeleton) with a hole, which can realize molecular recognition; the guest (denoted by G) is a compound (small molecule or ionophore) that is capable of being recognized by the host and inserted into the host's cavity. One host molecule may recognize a plurality of guest molecules bonded thereto, and in an embodiment of the present invention, it is preferable that one host molecule recognizes at most two guest molecules. The host molecules include, but are not limited to, ethers (including crown ethers, cryptates, globals, hemispheric ethers, pod ethers, lasso ethers, benzocrown ethers, heterocrown ethers, heterocryptates, mixed cryptates), cyclodextrins, cyclopolybdenes, cucurbiturils, calixarenes, column aromatics, and suitable inorganic-organic ionic backbones, preferably crown ethers, beta-cyclodextrins, cucurbiturils [8] urils, calixarenes, column [5] aromatics. The guest molecules include, but are not limited to, long chain alkanes, cycloalkanes, heterocycloalkanes, arenes, heteroarenes, fused ring structure compounds, heterocyclic structure compounds, monocyclic structure compounds, polycyclic structure compounds, spiro structure compounds, bridged ring structure compounds, suitable ionic groups, preferably long chain alkanes, heterocyclic compounds, polycyclic compounds, bridged ring compounds, suitable ionic groups. The host molecules and the guest molecules can exist stably in the polymer, the formed host and guest bodies have moderate action intensity and can interact or dissociate under milder conditions, so that the dynamic property of the polymer can be realized under usual conditions.

Suitable host molecules can be exemplified as follows, but the invention is not limited thereto:

Ni(PDC)(H ₂ O) ₂ skeleton, zn ₃ (PTC) ₂ (H ₂ O) ₈ ·4H ₂ An O skeleton;

suitable guest molecules can be exemplified as follows, but the invention is not limited thereto:

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

in the present invention, the term "metalphilic" refers to when the two outermost electron structures are d ¹⁰ Or d ⁸ The interaction force generated when the metal ions approach to less than the sum of the Van der Waals radii; wherein the two metal ions acting as a parent metal may be the same or different. The outermost electronic structure is d ¹⁰ Metal ions of (a) include, but are not limited to, cu ⁺ 、Ag ⁺ 、Au ⁺ 、Zn ²⁺ 、Hg ²⁺ 、Cd ²⁺ Preferably Au ⁺ 、Cd ²⁺ The method comprises the steps of carrying out a first treatment on the surface of the The outermost electronic structure is d ⁸ Metal ions of (a) include, but are not limited to Co ⁺ 、Ir ⁺ 、Rh ⁺ 、Ni ²⁺ 、Pt ²⁺ 、Pb ²⁺ Preferably Pt ²⁺ 、Pb ²⁺ . The metallophilic effect can exist in the polymer stably, has moderate action intensity, has certain directivity and no obvious saturation, can be aggregated to form polynuclear complex, is less influenced by 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 the present invention, the dipole-dipole action refers to an action of generating an electric dipole by causing an asymmetric distribution of electrons due to an uneven charge distribution caused by an induction action of atoms having a large electronegativity when two kinds of atoms having different electronegativity are bonded. The electric dipole may be generated by bonding any suitable two atoms having different electronegativity, for example, 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-I, H-O, H-S, H-N, preferably c≡ N, C = O, C-F, H-O, more preferably c≡n. Dipole-dipole interactions may be stably present in the polymer, easy to manipulate, pairing of the interacting groups may create a micro-domain, making the interactions more stable; at higher temperatures, the dipole-dipole effect will decrease or even disappear, and thus polymers containing dipole-dipole effect may exhibit dynamic differences depending on the temperature differences.

In the embodiment of the present invention, the combination between the 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 the present invention, the halogen bond action, which refers to a non-covalent interaction formed between a halogen atom and a neutral or negatively charged lewis base, is essentially an interaction between the sigma-back bond orbital of the halogen atom and an atom or pi-electron system having a lone pair of electrons. Halogen bond interactions may be represented by-X. Y-, wherein X may be selected from Cl, br, I, preferably Br, I; y may be selected from F, cl, br, I, N, O, S, pi bond, preferably Br, I, N, O. Halogen bonds have directional, linear-prone geometric characteristics; as the atomic number of halogen increases, the number of electron donors available for binding increases, and the strength of the halogen bond formed increases. Based on halogen bond action, ordered and self-repairing polymers can be designed.

In the embodiment of the present invention, the combination of the halogen bond forming atoms is not limited as long as a stable halogen bond forming action can be formed in the 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 the present invention, the lewis acid base pair 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 may be selected from a positive ion group (such as alkyl positive ion, nitro positive ion, quaternary ammonium positive ion, imidazole positive ion, etc.), a metal ion (such as sodium ion, potassium ion, calcium ion, magnesium ion, etc.), an electron-deficient compound (such as boron trifluoride, organoborane, aluminum chloride, ferric chloride, sulfur trioxide, dichloro carbene, trifluoro methane sulfonate, etc.), and the lewis acid is preferably alkyl positive ion, quaternary ammonium positive ion, imidazole positive ion, organoborane, more preferably organoborane; the Lewis base refers to a substance (comprising molecules, ions or atomic groups) capable of giving an electron pair and can be selected from negative ion groups (such as halide, oxide, sulfide, hydroxide, carbonate, nitrate, sulfate, phosphate, alkoxide, alkene, aromatic compound, etc.), compounds with a lone pair (e.g., ammonia, amines, imines, azo compounds, nitroso compounds, cyanides, isocyanates, alcohols, ethers, thiols, carbon monoxide, carbon dioxide, nitric oxide, nitrous oxide, sulfur dioxide, organophosphazenes, carbenes, etc.), the lewis base is preferably an alkoxide ion, an alkene, an aromatic compound, an amine, an azo compound, a nitroso compound, an isocyanate, carbon dioxide, an organophosphine, more preferably an amine, an azo compound, a nitroso compound, an organophosphine. Wherein the Lewis acid base pairing action is preferably a "hindered Lewis acid base pairing action", and the "hindered Lewis acid base pairing action" refers to that at least one of Lewis acid and Lewis base in the Lewis acid base pairing action needs to be connected with a large group with steric hindrance effect; the "bulky group having steric hindrance" can weaken the strength of coordination bond between Lewis acid and Lewis base, thereby making Lewis acid-base pair exhibit strong dynamic property of supermolecule, which is selected from C _3-20 Alkyl, ring C _3-20 Alkyl, phenyl, benzyl, aralkyl and unsaturated forms of the above groups, substituted forms, hybridized forms, and combinations thereof, more preferably from isopropyl, t-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 t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl. Wherein the azo compound is preferably selected from azomethane, azo tert-butane, N-methyl azomethylamine, N-methyl azoethylamine, N-ethyl azoethylamine, azodiacetic acid, azobenzene, azodiphenylamine, dichloroazobenzene, azodiisobutyronitrile, azodicarbonamide, dimethyl azodicarbonate, diethyl azodicarbonate, diisopropyl azodicarbonate and di-tert-butyl azodicarbonate; the nitroso compound is preferably selected from nitromethane, nitrosot-butane, N-nitrosoethanolamine, nitronitrobenzene, nitrosotoluene, nitrosochlorobenzene Nitrosonaphthalene, 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 an embodiment of the present invention, the formation combination of lewis acid-base pair action is not limited as long as 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:

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in the present invention, the term cation-pi-interaction refers to a non-covalent interaction formed between a cationic group and an aromatic pi-system. The cation-pi action is mainly of three general classes, the first group being simple inorganic cations or groups (e.g. Na ⁺ 、K ⁺ 、Mg ²⁺ 、NH ₄ ⁺ 、Ca ²⁺ ) And an aromatic pi system; the second group is the interaction between organic cations (such as quaternary ammonium cations) and aromatic pi systems; the third type is the interaction between positively charged atoms in the dipole bond (e.g., H atoms in the N-H bond) and the aromatic pi system. The cation-pi action is rich in variety and moderate in strength, can stably exist in various environments, and can prepare polymers with rich properties based on the cation-pi action.

In the embodiment of the present invention, the kind of cation-pi action is not particularly limited as long as a stable cation-pi action can be formed in the polymer. Some suitable cationic groups may be exemplified as follows, but the invention is not limited thereto:

Na ⁺ 、K ⁺ 、Li ⁺ 、Mg ²⁺ 、Ca ²⁺ 、Be ^{2 +} 、H-O、H-S、H-N。

in the present invention, the anionsPi-action, which refers to a non-covalent interaction formed between an anionic group and an electron-deficient aromatic pi-system. The anionic groups may be simple inorganic nonmetallic ions or ionic groups (e.g. Cl ^- 、Br ^- 、I ^- 、OH ^- ) The method comprises the steps of carrying out a first treatment on the surface of the Organic anionic groups (e.g., benzenesulfonic acid groups) are also possible; but also negatively charged atoms in the dipole bond (e.g., chlorine atoms in the C-Cl bond). The electron-deficient aromatic pi system refers to that pi electron cloud density distribution of a ring is uneven due to different electronegativity of ring forming atoms, pi electrons mainly shift towards the electronegativity high atomic direction, and accordingly pi electron cloud distribution density of an aromatic ring is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable recognition, and can be used for constructing polymers with special properties.

In the embodiment of the present invention, the kind of the anion-pi action is not particularly limited as long as a stable anion-pi action can be formed in the polymer. Some suitable anionic groups may be exemplified as follows, but the invention is not limited thereto:

Cl ^- 、Br ^- 、I ^- 、OH ^- 、SCN ^- ；

Some suitable electron-deficient aromatic pi systems may be exemplified as follows, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxa-calix [2] arene [2] triazine and benzene tricamide.

In the present invention, the benzene-fluorobenzene action refers to a non-covalent interaction composed of aromatic hydrocarbon and polyfluoroaromatic hydrocarbon through the combination of dispersion force and quadrupole action. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and the atomic radius are smaller, the fluorine atoms around in the polyfluoroaromatic hydrocarbon are negatively charged due to the large electronegativity, and the central carbocyclic ring skeleton is positively charged due to the smaller electronegativity. Because the electronegativity of the carbon atoms is greater than that of the hydrogen atoms, the direction of the electric quadrupole of the aromatic hydrocarbon is opposite to that of the electric quadrupole of the polyfluoroaromatic hydrocarbon, and because the volumes of the fluorine atoms are small, the polyfluoroaromatic hydrocarbon and the aromatic hydrocarbon are similar, the aromatic hydrocarbon and the polyfluoroaromatic hydrocarbon are piled in an alternating face-to-face mode to form a columnar piled structure, and the piled mode is basically not influenced by introduced functional groups. By utilizing the reversibility and accumulation of benzene-fluorobenzene action, a polymer with special functions can be prepared.

In the embodiment of the present invention, the kind of benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the polymer. Some suitable benzene-fluorobenzene actions can be exemplified as follows, but the invention is not limited thereto:

In the present invention, the pi-pi stacking effect refers to pi-pi stacking effect formed by overlapping pi-bond electron clouds, wherein the polymer contains an aromatic pi system capable of providing pi-bond electron clouds. There are three modes of action of pi-pi stacking, including face stacking, offset stacking, and side-face stacking. Wherein, the surface-surface accumulation refers to that the interacted annular surfaces are parallel to each other, the distance between the centers of the parallel annular surfaces and the distance between the annular surfaces are almost equal, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron attraction of the substituent groups connected on the annular surfaces is relatively strong, the pi-pi action of the surface-surface accumulation becomes relatively obvious; offset stacking refers to the fact that acting annular surfaces are parallel to each other, but the centers of the annular surfaces are offset to a certain extent, namely the distance between the annular surfaces is larger than the distance between the annular surfaces, and the stacking mode relieves the mutual exclusion action between the two annular surfaces, correspondingly increases the attraction of sigma-pi and is a common stacking mode; the stacking method other than the planar stacking and offset stacking is called edge-planar stacking, and this stacking method is the least energy and the least intermolecular repulsive force, and is often found between ring conjugated molecules having smaller van der Waals surfaces or between ring conjugated molecules having flexible linkers.

Aromatic pi systems capable of providing pi-bond electron clouds, including but not limited to most fused ring compounds and some heterocyclic compounds in which pi-pi conjugation is present, suitable aromatic pi systems are exemplified as, but the invention is not limited to, the following:

preferably->

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

In the embodiment of the present invention, the combination of aromatic pi systems providing pi-bond electron clouds is not particularly limited as long as a suitable pi-pi stacking effect is formed between the aromatic pi systems. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the ionic hydrogen bonding consists of a positive ionic group and a negative ionic group which can form hydrogen bonding, and simultaneously form hydrogen bonding and coulomb effect between positive and negative ions, or consists of a positive/negative ionic group and a neutral hydrogen bonding group which can form hydrogen bonding, and simultaneously form hydrogen bonding and ion-dipole effect between positive/negative ions and a neutral group.

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

In the present invention, the radical cationic dimerization refers to a supermolecular effect established by interactions between radical cationic groups containing both radicals and cations. By way of example, the free radical cationic groups that can form free radical cationic dimerization include, but are not limited to, the following:

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

in embodiments of the invention, the phase separation refers to the formation of incompatible phases between polymer segments having different chemical compositions, each due to incompatibility or compatibility with the environment. In the present invention, phase separation includes, but is not limited to, phase separation caused by incompatible polymer block structures in block polymer supermolecular monomers and phase separation caused by other supermolecular actions, preferably phase separation caused by incompatible polymer block structures in block polymer supermolecular monomers. Wherein, the crystallization in the present invention means that a part of the polymer segments may be aligned to form an ordered region, thereby being separated from other polymer segments of an amorphous form to form different phases. Crystallization is also a special phase separation. In the present invention, crystallization includes, but is not limited to, crystallization caused by the stereoregular easy-to-crystallize block in the block polymer supermolecular monomer and crystallization caused by liquid crystal and crystallization caused by other supermolecular actions, and preferably crystallization caused by the stereoregular easy-to-crystallize block in the block polymer supermolecular monomer and crystallization caused by liquid crystal.

The block structure capable of forming phase separation and/or crystallization described in the present invention means that the total number of blocks contained in a block polymer supermolecular monomer having a block structure is 2 or more, and at least two blocks may 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 included, the remaining blocks may form compatible or mutually incompatible phases with the other blocks, except that at least two of the blocks may form mutually incompatible phases.

In a preferred embodiment of the present invention, it is preferred that the block polymer supermolecular monomer comprises at least one hard segment and at least one soft segment. Wherein the hard segments are mixed with each other and/or each independently can form a crystalline phase and/or a phase incompatible with the soft segments to form phase-separated physical polymerization and/or cross-linking based on the hard segments; the phase formed by each soft segment is amorphous. The hard segment-based physical polymerization/crosslinking imparts similar physical properties to the polymer after covalent polymerization/crosslinking, including but not limited to apparent molecular weight increase, elasticity, dimensional stability, mechanical strength enhancement. Hard segment phase separated physical cross-linking is particularly suitable for providing the balanced structure, i.e. dimensional stability, of the polymers of the invention. Wherein more preferably at least two hard segments are connected to each other by soft segments, i.e. at least two hard segments and at least one soft segment form a hard segment-soft segment alternating structure to form a hard segment based phase separated physical cross-link, the crystallization/phase separation of the hard segments will more effectively form an inter-chain phase separated physical cross-link, which can effectively provide the strength of the phase separated physical cross-link, the equilibrium structure of the polymer and the mechanical properties of said physical phase separated polymer.

In another preferred embodiment of the present invention, preferably the block polymer supermolecular monomer is an amphiphilic polymer molecule comprising at least one solvophilic segment and at least one solvophobic segment; more preferably, at least two solvophobic segments are contained and are linked to each other by a solvophilic segment, i.e. at least two solvophobic segments and at least one solvophilic segment form a solvophobic segment-solvophilic segment alternating structure, to form a polymer gel.

In the embodiment of the present invention, the chain topology of the block polymer supermolecular 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 and branched structure. When a branched structure is present, a part of the hard/soft segments may be on the main chain and a part of the hard/soft segments may be on the side chains/branches/bifurcation chains.

In the embodiment of the invention, in the block polymer supermolecular monomer with both hard segments and soft segments, each hard segment can be the same or different, and each soft segment can be the same or different; wherein the hard segment and the soft segment may each independently comprise two or more identical or different sub-segments; the sub-chain segments can be smaller chain segments on the main chain, or smaller chain segments on side chains, branched chains and bifurcation chains; such differences include, but are not limited to, differences in chemical composition, molecular weight, topology, and spatial configuration. In the embodiments of the present invention, each of the hard segment, soft segment and its sub-segment may be a homopolymer segment or a copolymer segment, may be a homo-or co-polymer cluster, may be a cross-linked particle above the gel point of homo-or co-polymer, or may be a functional group or any combination of the above.

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 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 crosslinked particle structure, and 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 by at least one covalent bond or by a weak dynamic supramolecular interaction formed by a pair of supramolecular groups/units, preferably by one covalent bond. Wherein the covalent linkage may be a linker having a chemical structure different from that of the linked segment, the molecular weight of the linker being not higher than 1000Da, preferably the number of carbon atoms of the linker being not higher than 20, more preferably not higher than 10.

Taking as an example of the block polymer supermolecular monomer containing only two blocks of block A and block B, some preferable structures of the block polymer supermolecular monomer of the present invention as shown in the following formulas (a) to (e) can be cited, but the present invention is not limited thereto:

Wherein formula (a) is a linear structure, n is the number of alternating units of type A block-type B block, which is 0 or more; preferably n is 1 or more; the formula (B) is a linear structure, two end sections are A type blocks, n is the number of alternating units of A type blocks and B type blocks, 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, the other preferable 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 branching chain units of the type A block attached to the type B block B; n is the number of alternating units of the type A block-type B block, which is greater than or equal to 0; y is the number of branching chain units of the A-type block-B-type block attached to the B-type block B; x and y are equal to or greater than 0, and the sum of x and y is equal to or greater than 3; formula (d) is a branched structure, x is the number of branching chain units of the type A block attached to the type B block B; n is the number of alternating units of the type A block-type B block, which is greater than or equal to 0; y is the number of branching units which are linked alternately to the type A blocks-type B blocks and end-blocks of the type A blocks; x and y are equal to or greater than 0, and the sum of x and y is equal to or greater than 3; wherein, one preferable 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 preferable 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; the formula (e) is a cyclic structure, 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 1; preferably n is 2 or more. Among them, 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 are more preferable.

Furthermore, the block polymer supermolecular monomer structure of the present invention may be any combination of the above-listed preferred structures and any other suitable structure, and those skilled in the art may reasonably realize the logic and context according to the present invention.

In the present invention, the hard segments generally have a higher glass transition temperature and/or a crystalline phase formed and/or a phase formed by the soft segments has better thermal stability and/or higher mechanical strength and/or lower solubility than the soft segments and/or phases formed by the soft segments are incompatible with the soft segments. In an embodiment of the present invention, the supramolecular polymer comprising phase separation and/or crystallization typically has a soft phase comprising soft segments and a hard phase comprising hard segments in a two-phase structure; 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 "multiphase supramolecular polymer") may be present in the supramolecular polymer comprising phase separation and/or crystallization. In embodiments of the present invention, the phase topology (phase morphology) formed by the soft phase of soft segments and the hard phase of hard segments is not limited, including but not limited to spherical, cylindrical, helical, lamellar, and combinations thereof. Any one phase, including between different soft phases and between different hard phases, may be dispersed in another phase, may form an interpenetrating bi/multi continuous phase with other phases, or may be mutually independent continuous phases. In the embodiments 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 spherically dispersed in the soft phase, so that the multiphase supramolecular polymer can more conveniently have better softness and elasticity and be more suitable for exerting the dynamic properties of other supramolecular actions. The discontinuous hard phase typically has a size of 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 polymer is not particularly limited, and preferably comprises between 1% and 50% of the total weight, more preferably between 5% and 35% of the total weight, in order to facilitate the formation of efficient phase separation and/or crystalline cross-links.

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

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, a polymer segment having a main chain of a carbon chain structure, a carbon hybrid chain structure, a carbon element chain structure, an element hybrid chain structure, a carbon hybrid element chain structure, and other supermolecular action units. The carbon chain structure is a structure with a main chain skeleton containing only carbon atoms; the carbon hetero-chain structure is a structure with a main chain skeleton containing carbon atoms and any one or more hetero atoms, wherein the hetero atoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure with a main chain skeleton containing 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 hetero-chain structure is a structure with a main chain skeleton and at least one hetero atom and at least one element atom; the carbon hetero element chain structure is a structure that a main chain skeleton simultaneously comprises carbon atoms, hetero atoms and element atoms. Among them, carbon chain structure and carbon hybrid chain structure are preferable, and the industrial preparation technology is mature because of easy availability of raw materials. By way of example, the hard segments of the polymer may be segments based on, but not limited to, the following polymer segments, groups, or any combination thereof: amorphous polymer segments having a high glass transition temperature, such as polystyrene, polyvinylpyridine, hydrogenated polybornene, polyetheretherketone, polyaromatic carbonate, polysulfone, 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 polyester, crystalline polyether, liquid crystalline polymers (such as poly-p-benzamide, poly-p-phenylene terephthalamide, polybenzothiazole, polybenzoxazole, etc.), liquid crystalline groups (such as azobenzene and its derivatives, biphenyl, diphenyl terephthalate, cholesteric derivatives, etc.). Wherein the crystallization refers to a process of forming an ordered region by arranging polymer chains, and comprises crystallization caused by supermolecule action such as coordination, compounding, assembly, combination, aggregation and the like, crystallization caused by incompatible phases, crystallization caused by incompatible block structures, crystallization caused by regular and easy-to-crystallize chain segments, crystallization caused by liquid crystals and the like. Among them, the introduction of a liquid crystal segment and the utilization of crystallization caused by liquid crystal are preferable because crystallization can be effectively controlled so that it can be dynamically and reversibly converted under the stimulation conditions of heat, light, pH, chemical changes, and the like.

In an embodiment of the present invention, the soft segment polymer skeleton may be selected from, but not limited to, a polymer chain segment whose main chain is a carbon chain structure, a carbon hybrid chain structure, a carbon element chain structure, an element hybrid chain structure, a carbon hybrid element chain structure, and may be other supermolecular action units, preferably a carbon chain structure, a carbon hybrid chain structure, an element hybrid chain structure, and a carbon hybrid element chain structure, because of easy availability of 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: homopolymers or copolymers of acrylic polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, silicone polymers, polyether polymers, polyester polymers, biopolyester polymers, and the like.

In embodiments of the present invention, the hard phase of the multiphase supramolecular polymer may have no glass transition temperature or one or more glass transition temperatures and may also have one or more split-phase physical crosslinking temperatures, preferably the split-phase physical crosslinking temperature of any hard segment is above the upper end of the operating temperature range; the soft phase of the multiphase supramolecular polymer may also have no glass transition temperature or one or more glass transition temperatures, preferably wherein at least one glass transition temperature is not higher than the lower limit of the operating temperature range; when the multiphase supermolecular polymer contains auxiliary agents or fillers such as plasticizer and the like so that at least one glass transition temperature of a soft segment is not higher than the lower limit of the working temperature range, and simultaneously 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 supermolecular polymer.

In embodiments of the present invention, the block polymer supermolecular monomer may contain other supermolecular groups/units together. The positions of other supermolecule groups/units are not limited, and the supermolecule groups/units can be positioned at the connection positions of hard segments and/or soft segments and/or hard segments and soft segments, and are selected to be positioned at the connection positions of soft segment main chain frameworks and/or soft segment side groups and/or soft segment end groups and/or soft segments and hard segments, in particular to the connection positions of soft segment side chain frameworks/side groups/end groups, which is more beneficial to reflecting the dynamic nature of the actions of other supermolecules.

In the present invention, the polymer may contain one or more of the non-covalent interactions/supramolecular interactions. When multiple classes of non-covalent interactions are involved, it is preferred that the multiple classes of non-covalent interactions/supramolecular interactions have orthogonality and/or synergy. Said orthogonality means that the formation, dissociation and other responses of said plurality of different non-covalent interactions/supramolecular interactions with each other do not affect each other; by synergistic, it is meant that the formation and/or dissociation and/or other response of one or more of the different non-covalent interactions/supramolecular interactions triggers or occurs simultaneously with the formation and/or dissociation and/or other response of the other non-covalent interactions/supramolecular interactions and produces a greater effect than the linear superposition of the various non-covalent interactions/supramolecular interactions.

In the present invention, non-covalent dynamics/supramolecular dynamics of non-covalent interactions/supramolecular interactions refers to the rate of transition between its dissociated and associated/bound states, the faster the rate the more dynamic.

In the invention, the weak dynamic non-covalent crosslinking generally has higher bonding strength, so that the mechanical strength and modulus of the material are conveniently improved, and the weak dynamic non-covalent crosslinking can be used as a sacrificial bond to absorb impact energy, improve toughness and improve damage resistance. The strong dynamic non-covalent crosslinking has the advantages that the exchange speed is high, and non-covalent motifs at different positions can be exchanged and recombined, so that more excellent dynamic dilatant performance is obtained, the low-temperature hardening process of the dilatant polymer can be effectively inhibited, the sensitivity of the dilatant to temperature is reduced, the positive effect on the dilatant performance at low temperature is achieved, and the microcosmic self-repairing process of the material and the tear resistance of the material can be accelerated.

According to the invention, based on the non-covalent dynamic property/supermolecular dynamic property of the non-covalent action/supermolecular action, other properties of the polymer, such as directionality of halogen bond action, controllable selectivity and controllable recognition of small molecules/ions/groups in cation-pi action, anion-pi action and host-guest action, benzene-fluorobenzene action, ordering of pi-pi stacking action, pH, concentration sensitivity, conductivity, temperature sensitivity of dipole-dipole action, metal-philic interaction, special photo-electric property of free radical cation dimerization and the like can be obtained, and non-covalent element/supermolecular element can be reasonably selected for molecular design according to requirements, so that the unique functional characteristics of the polymer material are provided. These represent the benefits and creativity of the present invention.

In embodiments of the present invention, the term "non-covalent moiety/supermolecule moiety" refers to a group or molecule or structural unit that is used to form various types of non-covalent interactions/supermolecular interactions, including, but not limited to, hydrogen bonding groups, ligand groups, metal centers, ionic groups, electric dipoles, host molecules, guest molecules, metal ions, halogen atoms, lewis bases, lewis acids, aromatic pi systems, aromatic hydrocarbons, polyfluoroaromatic hydrocarbons, free radical cationic groups, phase-separated polymer segments, crystalline polymer segments, and the like. The non-covalent/supramolecular motifs may be located at any suitable position on the polymer, including, but not limited to, on the cross-linked network chain backbone of the cross-linked polymer, on the side/branched/forked chain backbone of the cross-linked network chain backbone of the cross-linked polymer, on the side and/or end groups of the polymer, on other constituent components of the polymer such as small molecules, fillers, etc.

In embodiments of the present invention, one or more non-covalent/supramolecular motifs may be contained in the same polymer, or one or more non-covalent/supramolecular motifs may be contained in the same crosslinked network, i.e., one non-covalent/supramolecular motif or a combination of non-covalent/supramolecular motifs may be contained in the polymer. The non-covalent motifs/supramolecular motifs may be introduced by any suitable chemical reaction, for example: isocyanate reacts with amino, hydroxyl, sulfhydryl and carboxyl, the nucleophilic substitution reaction of heterocycle, double bond free radical reaction, the side chain reaction of heterocycle, azide-alkyne click reaction, sulfhydryl-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, and the reaction of active ester with amino; preferably isocyanate with amino, hydroxyl, sulfhydryl, azide-alkyne click reactions, urea-amine reactions, amidation reactions, reactive ester with amino, sulfhydryl-double bond/alkyne click reactions; more preferably isocyanate with amino, hydroxyl, mercapto-double bond/alkyne click reaction, azide-alkyne click reaction.

In embodiments of the present invention, the non-covalent motifs/supramolecular motifs may be incorporated in any suitable composition and at any suitable timing, including but not limited to from monomers, while forming the prepolymer, after forming the prepolymer, while forming the cross-links, and after forming the cross-links. Preferably at the same time as the prepolymer and crosslinking are formed. In order to avoid the operations of mixing, dissolving and the like caused by the formation of non-covalent crosslinking/supermolecular crosslinking after the introduction of the non-covalent motifs/supermolecular motifs, the non-covalent motifs/supermolecular motifs can also be blocked and protected, and then deprotected for a suitable time (e.g. simultaneously or after the formation of crosslinking).

In embodiments of the present invention, typical weakly dynamic covalent bonds include, but are not limited to: dynamic continuous sulfur bond, dynamic continuous selenium bond, dynamic selenium sulfur bond, dynamic selenium nitrogen bond, acetal dynamic covalent bond, dynamic covalent bond based on carbon-nitrogen double bond, combined exchangeable acyl bond, dynamic covalent bond based on steric effect induction, 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 generating alkene cross metathesis reaction, unsaturated carbon triple bond capable of generating alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond, mercapto-Michael addition dynamic covalent bond, amine alkene-Michael addition dynamic covalent bond, dynamic covalent bond based on triazoline diketone-indole, dynamic covalent bond based on diazacarbene, benzoyl-based dynamic covalent bond, hexahydrotriazine dynamic exchangeable trialkylsulfonium bond, dynamic covalent bond of diketone enamine. The dynamic covalent bond with weak dynamic property generally does not generate dynamic bonding-dissociation balance under the conditions of material working temperature, no external field effect and the like, can provide better structural stability, can generate dynamic reversible transformation under specific stimulation effect/dynamic conditions (such as heating, illumination, specific pH, catalyst, redox agent and the like), obtains dynamic covalent characteristics, realizes the uncrosslinking of a dynamic crosslinked structure, causes the change of a polymer chain structure and a topological structure, and therefore realizes the molecular level and microscopic self-repairing performance on material damage, obtains shape memory performance, improves the comprehensive mechanical property and energy absorption performance of the material and the like.

In embodiments of the present invention, typical weak dynamic non-covalent interactions include, but are not limited to: hydrogen bonding, metal-ligand, phase separation, crystallization of three or more teeth. The weak dynamic supermolecular action/non-covalent action is generally not reversibly transformed under the conditions of material working temperature, no external field action and the like, is convenient for providing good structural stability, can dynamically and reversibly transform under specific stimulation action/dynamic conditions (such as actions of heating, illumination, specific pH and the like), obtains non-covalent dynamic/supermolecular dynamic, realizes the uncrosslinking of a non-covalent crosslinking structure, causes the change of a polymer chain structure and a topological structure, and thereby realizes the molecular level and microscopic self-repairing performance on material damage, obtains shape memory performance, improves the comprehensive mechanical property and energy absorption performance of the material and the like.

In the present invention, the kind and the number of the dynamic units contained in the dilatant hybrid dynamic polymer are not particularly limited. That is, the dilatant hybrid dynamic polymer may contain only one dynamic covalent bond or only one non-covalent effect/supramolecular effect, or at least two dynamic covalent bonds or at least two non-covalent effects/supramolecular effects, or one dynamic covalent bond and one non-covalent effect/supramolecular effect, or one dynamic covalent bond and at least two non-covalent effects/supramolecular effects; or at least two dynamic covalent bonds and one non-covalent/supramolecular effect; or at least two dynamic covalent bonds and at least two non-covalent/supramolecular interactions simultaneously; but the present invention is not limited thereto. Those skilled in the art can reasonably select and use the materials according to the present invention to obtain more practical dynamic reversible performance, self-repairing performance, other use performance, etc.

In the invention, two or more dynamic units, especially dynamic units with different stimulus responsivity/dynamic reversible conditions, are introduced into the dilatant hybrid dynamic polymer, so that the dynamic performance with orthogonality and multiple stimulus responsivity can be obtained, and the shape memory function can be obtained. In a preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form dynamic crosslinking, wherein one dynamic unit has light responsiveness, the other dynamic unit does not have light responsiveness, the dynamic reversible transformation of the former dynamic unit is induced by illumination, and the decrosslinking is realized, namely, temporary shaping effect is obtained, and the latter dynamic crosslinking can play a permanent shaping effect due to the fact that the dynamic crosslinking does not have light responsiveness, so that the shape memory performance of the dilatant polymer material is provided together. In another preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form a dynamic crosslinking effect, wherein the two dynamic units have photo-responsivity, but the photo-responsivity wavelength ranges of the two dynamic units are different, and the temporary shaping effect is obtained by regulating and controlling the irradiation wavelength to induce the de-crosslinking of part of the dynamic crosslinking effect, while the other dynamic crosslinking effect can play the role of permanent shaping and jointly provide the shape memory property of the dilatant polymer material because the other dynamic crosslinking effect can not generate dynamic reversible transformation under the irradiation of the wavelength. In another preferred embodiment of the present invention, two dynamic units are introduced into the dilatant hybrid dynamic polymer and used as crosslinking connection points to form a dynamic crosslinking effect, wherein the two dynamic units have temperature responsiveness, but the response temperatures of the two dynamic units are different, and the temporary shaping effect is obtained by regulating and controlling the temperature to induce the decrosslinking of part of the dynamic crosslinking effect, while the other dynamic crosslinking effect can play a role of permanent shaping because the dynamic crosslinking effect cannot be dynamically and reversibly converted at the temperature, so that the shape memory performance of the dilatant polymer material is provided together.

In the invention, the dilatant hybrid dynamic polymer can be uniform or have a gradual structure/gradient structure, so that the dynamic performance with gradual change/gradient change is obtained, and the requirements of different application scenes are met. In a preferred embodiment of the invention, the cross-linking density of the dilatant hybrid dynamic polymer is graded to achieve graded/graded mechanical properties. In another preferred embodiment of the present invention, the cross-linking point strength of the dilatant hybrid dynamic polymer is graded to achieve graded mechanical properties. In another preferred embodiment of the present invention, the distribution and/or dynamic binding strength of the weakly dynamic units in the dilatant hybrid dynamic polymer is graded to achieve graded/graded dynamic and mechanical properties.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bonds.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the dynamic covalent bond above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains dynamic covalent bonds.

The dynamic covalent bond contained in the dilatant hybrid dynamic polymer is an essential structural factor for endowing the dilatant hybrid dynamic polymer with molecular level and microscopic self-repairing performance. In addition, the introduction of the dynamic covalent bond can also be used as a sacrificial bond to absorb energy and improve toughness and damage resistance. In particular, a weak dynamic covalent cross-linking above the gel point is introduced into the polymer, which can also provide a shape memory function to the polymer together with a common covalent cross-linking; the high dynamic covalent crosslinking is introduced into the polymer, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like. The dilatant hybrid dynamic polymer can only contain one dynamic covalent bond or a plurality of dynamic covalent bonds, and the dynamic strength of the dynamic covalent bonds can be reasonably selected and combined according to the use requirement so as to achieve the optimal performance and meet the requirements of various different application scenes, thereby embodying the creativity and novelty of the invention.

In a preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from boron-containing dynamic covalent bonds. In the embodiment, the boron-containing dynamic covalent bond has the characteristics of high dynamic reversible speed, high dynamic property and the like, can endow the material with dynamic dilatancy, improves the low-temperature dilatancy of the material and accelerates the self-repairing process of the material. Another more preferred embodiment is that the boron-containing dynamic covalent bond is selected from saturated five-membered ring organoborate bond, unsaturated five-membered ring organoborate bond, saturated six-membered ring organoborate bond, unsaturated six-membered ring organoborate bond, inorganic borate bond, organoborate bond, dynamic titanate bond, which has stronger dynamic property and is easier to enhance dynamic dilatancy.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from boron-free dynamic covalent bonds. In the embodiment, the boron-free dynamic covalent bonds are various in variety, have various characteristics of rich respective dynamic and stimulus responsiveness, reasonably design and select the variety and the number of the dynamic covalent bonds, and can better meet the requirements of different application scenes on the dilatancy, the self-repairing property and other use performances of the dilatant material.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from dynamic covalent bonds based on reversible free radicals. In the embodiment, the dynamic covalent bond based on the reversible free radical has rich structural characteristics, and thus, the dynamic covalent bond shows rich dynamic property and stimulus responsiveness, and can provide dynamic dilatancy for the polymer and realize a shape memory function through proper dynamic stimulus action.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from dynamic acid ester linkages. In the embodiment, the dynamic acid ester bond has the characteristic of strong dynamic property, and can improve the low-temperature dilatancy of the material.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from the group consisting of dynamic sulfide bonds, dynamic selenium sulfide bonds, reversible addition fragmentation chain transfer dynamic covalent bonds, thiol-michael addition dynamic covalent bonds, amine alkene-michael addition dynamic covalent bonds. In the embodiment, the dynamic covalent bond has the characteristics of higher dynamic bonding strength, weaker dynamic property and the like, and is beneficial to improving the mechanical properties of the material, such as toughness and damage resistance of the material, and taking the material as a sacrificial bond for energy absorption and the like. The dynamic response conditions of the dynamic covalent bond are rich, especially the dynamic stimulus response to the actions of heating, illumination, redox agents and the like, the molecular level and microcosmic self-repairing of the structural damage of the material can be better realized, the shape memory function is realized through reasonable regulation and control of the cross-linking structure and the cross-linking degree of the polymer, and the application field of the dilatant material is further expanded.

In another preferred embodiment of the present invention, the dynamic covalent bond contained in the dilatant hybrid dynamic polymer is selected from the group consisting of [2+2] cycloaddition dynamic covalent bond, [4+2] cycloaddition dynamic covalent bond and [4+4] cycloaddition dynamic covalent bond. In the embodiment, the dynamic covalent bond has the characteristics of higher dynamic bonding strength, weaker dynamic property and the like, and is beneficial to improving the mechanical properties of the material, such as toughness and damage resistance of the material, and taking the material as a sacrificial bond for energy absorption and the like. The dynamic response conditions of the dynamic covalent bond are rich, especially the dynamic stimulus response to the actions of illumination, heating and the like, and the molecular level and microcosmic self-repairing of the material structure damage can be better realized.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a dynamic covalent bond comprising boron and a dynamic covalent bond comprising no boron. In the embodiment, at least two dynamic covalent bonds are introduced into the polymer, so that the synergistic and/or orthogonal dynamic property and stimulus responsiveness are conveniently obtained, the synergistic self-repairing process is realized, or the self-repairing process can be quickly and efficiently obtained by carrying out self-repairing under various conditions, so that the material has more practicability.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond, wherein the boron-free dynamic covalent bond has a strong dynamic property. In the embodiment, at least two strong dynamic covalent bonds are introduced into the polymer, so that the dynamic dilatancy of the material can be further enriched, and a rapid self-repairing process is realized.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond, wherein the boron-free dynamic covalent bond has a weak dynamic property. In this embodiment, the boron-free dynamic covalent bond has weak dynamic properties so as to form differential dynamic properties with the boron-containing dynamic covalent bond in the polymer, and the dynamic dilatancy, self-repairing property and other properties of the material, such as dynamic bonding strength, material toughness, tear resistance and the like, are better balanced. Dynamic covalent bonds with strong and weak dynamic properties are introduced into the polymer, and the comprehensive energy absorption performance of the material can be better improved.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises at least two dynamic covalent bonds, preferably the dynamic covalent bonds have orthogonal dynamics. In this embodiment, the two dynamic covalent bonds have orthogonal dynamics, so that they can realize dynamic response under the action of various dynamic stimuli, and perform multi-path microscopic self-repair on the damage of the polymer structure. Another more preferred embodiment is that both dynamic covalent bonds have weak dynamics to better achieve shape memory and multiple shape memory.

The dynamic covalent bond contained in the dilatant hybrid dynamic polymer can all play a role in crosslinking to form dynamic covalent crosslinking; it is also possible to carry out only polymerization, grafting, functionalization, etc. without crosslinking; and the partial dynamic covalent bond can play a role in crosslinking and the partial dynamic covalent bond can not play a role in crosslinking. In the embodiment of the invention, the dynamic covalent bonds preferably play a role in crosslinking so as to improve the mechanical property, dilatant property, self-repairing property and comprehensive energy absorption property of the material.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

The single network structure can be a common covalent cross-linked network or a hybridization cross-linked network, and the cross-linking degree of the common covalent cross-linking is above the gel point; in the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms having at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a hybrid cross-linked network and a dynamic covalent cross-linked network, a combination of two hybrid cross-linked networks.

The dilatant hybrid dynamic polymer with a single network structure or a multi-network structure contains at least one vitrified dilatant polymer component so as to obtain vitrified dilatant. In addition, the dilatant hybrid dynamic polymer can also optionally contain dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure so as to enrich dilatant of dilatant polymer.

The non-crosslinked structure can be dispersed in the dilatant hybrid dynamic polymer with a single network structure or a multi-network structure, preferably the non-crosslinked dilatant polymer is selected, more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic covalent bond, so that the extra dynamic dilatant is conveniently obtained, the viscous flow of the chain segment is also convenient, and the energy absorption performance is further improved.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has the advantages that the energy absorbing mechanism is very rich, besides the traditional energy absorbing mechanism, the energy absorbing method also comprises the steps of energy absorption through the dilatancy of the polymer, energy absorption through the dynamic reversible transformation process of the dynamic covalent bond contained in the polymer and the like as a sacrificial bond, and the energy absorbing method can provide excellent energy absorbing performance for the polymer energy absorbing material and perform effective impact resistance protection, thereby solving the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the non-hydrogen bond supermolecular action above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function.

Non-hydrogen bond supramolecular interactions as described herein refer to supramolecular interactions other than hydrogen bonding, which include, but are not limited to, metal-ligand interactions, ionic interactions, ion-cluster interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bond interactions, lewis acid base pairing interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ion hydrogen bonding interactions, radical cation dimerization interactions.

In the embodiment of the invention, the non-hydrogen bond supermolecule has various types of actions, rich dynamic property and stimulus response, and can obtain synergistic and/or orthogonal non-covalent dynamic property by introducing the non-hydrogen bond supermolecule into a polymer, so that the abundant dynamic dilatant property can be obtained more easily, and the comprehensive mechanical property of the dilatant material, especially the tear resistance and toughness of the material, can be improved.

In a preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect. In the embodiment, through reasonably selecting proper ligand groups and metal centers, non-covalent effects with different dynamics can be obtained, and the requirements of different application scenes on the dilatancy and the dynamics of the material are met.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises bidentate and below metal-ligand interactions. In the embodiment, the metal-ligand effect with the number of teeth of two teeth or less has the characteristic of strong dynamic property, can endow the polymer with dynamic dilatant, can accelerate microscopic self-repairing property of the material and improves tear resistance.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises tridentate and more metal-ligand interactions. In the embodiment, the metal-ligand effect has the characteristics of higher dynamic bonding strength and weaker dynamic property, is favorable for improving the mechanical properties of the material, such as toughness and damage resistance of the material, takes the material as a sacrificial bond to absorb energy and the like, and can realize the shape memory function through reasonable regulation and control of the cross-linking structure and the cross-linking degree of the polymer, thereby further expanding the application field of the dilatant material.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a combination of bidentate and less bidentate metal-ligand interactions with tridentate and more tridentate metal-ligand interactions. This embodiment may better balance the non-covalent dynamics, microscopic self-repairing, dynamic dilatancy, and other properties of the material, such as dynamic bond strength, material toughness, tear resistance, etc.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises ionic interactions. In the embodiment, through reasonably selecting proper positive ion groups and negative ion groups, rich ion effects can be obtained, dynamic dilatancy and non-covalent dynamic properties are provided for the polymer, microscopic self-repairing of material damage is realized, and tear resistance is improved. In addition, the introduction of the positive ion groups and the negative ion groups into the polymer is also helpful to improve the antibacterial property of the material, so that the dilatant material is safer and more sanitary in the use process.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a host-guest effect. In the embodiment, by reasonably selecting proper host and guest molecules/groups, rich host-guest actions can be obtained, the polymer is endowed with strong dynamic property and dynamic stimulus responsiveness, and the self-repairing of dynamic dilatancy and accelerated material damage is realized. In addition, the host-guest effect has special controllable selectivity and controllable recognition on small molecules/ions/groups, and the use function of the dilatant material can be further expanded.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises lewis acid base pairs. In the embodiment, through reasonably selecting Lewis acid and Lewis base molecules/groups, abundant Lewis acid-base interaction can be obtained, the non-covalent dynamic property of the dilatant polymer is endowed, and the self-repair of dynamic dilatant and accelerated material damage is realized.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises pi-pi stacking. In the embodiment, the condensed ring compound and the pi-pi conjugated heterocyclic compound are reasonably selected, so that an ordered pi-pi stacking effect can be obtained, and dynamic dilatancy and tear resistance of the dilatant polymer are provided.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a benzene-fluorobenzene action. In this embodiment, in addition to providing dynamic dilatancy to the polymer by utilizing the strong dynamic nature of the benzene-fluorobenzene action, dilatancy polymers with specific functions can be prepared based on their specific reversibility and ordered stacking characteristics.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding. In the embodiment, the ionic hydrogen bonding has the characteristics of both hydrogen bonding and ionic bonding, and the polymer has rich stimulus responsiveness, such as sensitivity to pH, concentration and the like, and can reach a required state by regulating the pH and the concentration.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding. In this embodiment, the ion-dipole effect has strong dynamic property, dynamic dilatancy can be realized, and is sensitive to pH, concentration and the like, and the polymer can be brought to a desired state by adjusting and controlling the pH and the concentration.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer contains halogen linkages. In the embodiment, the halogen bond function has strong dynamic property, can realize dynamic dilatant property, has special directivity, and can expand the functional application of the dilatant material.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a cation-pi-effect or an anion-pi-effect. In the embodiment, the cation-pi action and the anion-pi action have strong dynamic property, so that dynamic dilatancy can be realized, and the non-hydrogen bond supermolecule action also has special controllable selectivity and controllable recognition property on small molecules/ions/groups, so that the use function of the dilatancy material can be expanded.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metallophilic interaction or a free radical cationic dimerization. In the embodiment, the metal-philic interaction and the free radical cation dimerization have strong dynamic property, dynamic dilatancy can be realized, and the photoelectric property of the dilatancy material can be expanded based on the special photoelectric property of the non-hydrogen bond supermolecule effect.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises at least two non-hydrogen bonding supramolecular interactions and at least one of the non-hydrogen bonding supramolecular interactions is a metal-ligand interaction, preferably the metal-ligand interaction is a tridentate or more metal-ligand interaction. In this embodiment, at least two non-hydrogen bond supermolecular interactions are introduced into the dilatant hybrid dynamic polymer and at least one has weak dynamics, so that synergistic and/or orthogonal dynamics and stimulus responsiveness are conveniently obtained, and dynamic binding strength and dynamic dilatancy are easily balanced. Based on the difference characteristics of dynamic strength of the contained non-hydrogen bond supermolecule effect, the non-covalent dynamic property, microcosmic self-repairing property and other properties of the material, such as dynamic bonding strength, material toughness, tear resistance and the like, can be balanced better.

The non-hydrogen bond supermolecular effect contained in the dilatant hybrid dynamic polymer is an essential structural factor for endowing the dilatant hybrid dynamic polymer with molecular level and microscopic self-repairing performance. In addition, the introduction of non-hydrogen bond supermolecule function can also be used as a sacrificial bond to absorb energy and improve toughness and damage resistance. In particular, weak dynamic non-hydrogen bond supermolecule action above gel point, such as metal-ligand action with number of teeth above tridentate, is introduced into the polymer, and can also be used for providing shape memory function for the polymer together with common covalent crosslinking; the high dynamic non-hydrogen bond supermolecule effect is introduced into the polymer, so that the dynamic and dynamic dilatancy can be provided, the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material can be improved, and the like. The dilatant hybrid dynamic polymer can only contain one or a plurality of non-hydrogen bond supermolecule actions, and the dynamic strength of the non-hydrogen bond supermolecule actions can be reasonably selected and combined according to the use requirement so as to achieve the optimal performance, and can meet the requirements of various different application scenes, thereby embodying the creativity and novelty of the invention.

The non-hydrogen bond supermolecule contained in the dilatant hybrid dynamic polymer acts as a crosslinking function to form non-hydrogen bond supermolecule crosslinking; it is also possible to carry out only polymerization, grafting, functionalization, etc. without crosslinking; it is also possible that part of the non-hydrogen bond supermolecule acts as cross-linking and part of the non-hydrogen bond supermolecule acts as non-cross-linking. In the embodiment of the invention, the non-hydrogen bond supermolecule function preferably plays a role in crosslinking so as to improve the mechanical property, dilatant property, self-repairing property and comprehensive energy absorption property of the material.

In the invention, the term "non-hydrogen bond supermolecule crosslinking" refers to a crosslinking structure formed by the joint participation of non-hydrogen bond supermolecule action and common covalent bonds, and the crosslinking degree of common covalent crosslinking in a crosslinking network is below the gel point (common covalent crosslinking does not exist in the crosslinking network), wherein the crosslinking formed by the non-hydrogen bond supermolecule action is a necessary condition for forming the crosslinking network; based on the reversible characteristic of the non-hydrogen bond supermolecule crosslinking, the formed crosslinked network can carry out dissociation-bonding balance of the crosslinked network under proper conditions, and the dynamic reversibility is shown. The crosslinked network formed by the non-hydrogen bond supermolecule crosslinking is the non-hydrogen bond supermolecule crosslinked network. It should be noted that when the non-hydrogen bond supermolecule crosslinked network contains two or more non-hydrogen bond supermolecules and at least one of the non-hydrogen bond supermolecules is a weak dynamic non-hydrogen bond supermolecule, the non-hydrogen bond supermolecule crosslinked network is regarded as a weak dynamic non-hydrogen bond supermolecule crosslinked network; when the non-hydrogen bond supermolecule crosslinked network contains two or more non-hydrogen bond supermolecule actions and all the non-hydrogen bond supermolecule actions are strong dynamic non-hydrogen bond supermolecule actions, the non-hydrogen bond supermolecule crosslinked network is regarded as the strong dynamic non-hydrogen bond supermolecule crosslinked network.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

The single network structure can be a common covalent cross-linked network or a hybridization cross-linked network, and the cross-linking degree of the common covalent cross-linking is above the gel point; in the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms having at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a hybrid cross-linked network and a non-hydrogen bonding supramolecular cross-linked network, a combination of two hybrid cross-linked networks.

The dilatant hybrid dynamic polymer with a single network structure or a multi-network structure contains at least one vitrified dilatant polymer component so as to obtain vitrified dilatant. In addition, the dilatant hybrid dynamic polymer can also optionally contain dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure so as to enrich dilatant of dilatant polymer.

The non-crosslinked structure can be dispersed in the dilatant hybrid dynamic polymer with a single network structure or a multi-network structure, preferably the non-crosslinked dilatant polymer is selected, more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic non-hydrogen bond supermolecule effect, so that the extra dynamic dilatant can be conveniently obtained, and the viscous flow of the chain segment can be conveniently realized, thereby further improving the energy absorption performance.

Compared with the traditional polymer energy-absorbing material and the energy-absorbing method thereof, the energy-absorbing method has the advantages that the energy-absorbing mechanism is very rich, the energy-absorbing method also comprises the steps of energy absorption through the dilatancy of the polymer, dynamic reversible transformation process through the non-hydrogen bond supermolecular effect contained in the polymer, energy absorption through the sacrificial bond and the like, and can provide excellent energy-absorbing performance for the polymer energy-absorbing material and effectively absorb energy, resist impact and protect, so that the problems of single energy-absorbing mechanism, poor energy-absorbing effect and the like of the traditional energy-absorbing material are solved. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function and hydrogen bond function.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the non-hydrogen bond supermolecular action and the hydrogen bond action above the gel point are simultaneously introduced, so that the vitrification dilatancy and the optional dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains non-hydrogen bond supermolecule function and hydrogen bond function.

The non-hydrogen bond supermolecular action and the hydrogen bond action contained in the dilatant hybrid dynamic polymer are necessary structural factors for endowing the dilatant hybrid dynamic polymer with molecular level and microscopic self-repairing performance.

The hydrogen bond action contained in the dilatant hybrid dynamic polymer can be the hydrogen bond action of the number of teeth below two teeth or the hydrogen bond action of the number of teeth above three teeth, and can also comprise at least one hydrogen bond action of the number of teeth below two teeth and at least one hydrogen bond action of the number of teeth above three teeth; the hydrogen bonding action of the two teeth and the teeth below the two teeth has strong dynamic property, and can provide dynamic dilatancy for the polymer and rapid microcosmic self-repairing of material damage; the three-tooth or more tooth number hydrogen bonding action has weak dynamic property, not only provides weak dynamic property and microcosmic self-repairing property of material damage for the polymer, but also can be used as a sacrificial bond to absorb energy and improve toughness and damage resistance; the combination of the hydrogen bonding action of the teeth below two teeth and the hydrogen bonding action of the teeth above three teeth can better balance the mechanical property, the dynamic dilatancy, the microscopic self-repairing property and the like of the material.

In the embodiment of the invention, the non-hydrogen bond supermolecule function is various in variety, rich in dynamic property and stimulus response, and the non-hydrogen bond supermolecule function and the hydrogen bond function are introduced into the polymer, so that the synergetic and/or orthogonal non-covalent dynamic property can be obtained, the rich dynamic dilatant property can be obtained more easily, and the comprehensive mechanical property, the dynamic dilatant property and the microscopic self-repairing property of the material can be balanced better.

In a preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises a metal-ligand interaction and a hydrogen bonding interaction.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises ionic and hydrogen bonding.

In another preferred embodiment of the invention, the dilatant hybrid dynamic polymer comprises host-guest interactions and hydrogen bonding interactions.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises halogen bonding and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises lewis acid base pairing and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises benzene-fluorobenzene action and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises ionic hydrogen bonding and hydrogen bonding.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect of three or more teeth and hydrogen bonding effect of two or less teeth. In the embodiment, the strong dynamic hydrogen bonding effect can provide dynamic dilatant for the polymer, the weak dynamic metal-ligand effect can provide good dynamic bonding strength for the polymer, and the strong dynamic metal-ligand effect and the weak dynamic metal-ligand effect can synergistically improve the toughness and tear resistance of the material and better realize microscopic self-repairing when the dilatant material is damaged.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises metal-ligand interactions of two or less teeth and hydrogen bonding interactions of three or more teeth. In the embodiment, the metal-ligand effect with strong dynamic property can provide dynamic dilatancy for the polymer, the hydrogen bond effect with weak dynamic property can provide good dynamic bonding strength for the polymer, and the metal-ligand effect with strong dynamic property can enhance the toughness and tear resistance of the material and better realize microscopic self-repairing when the dilatancy material is damaged.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises metal-ligand interactions with and hydrogen bonding interactions with bidentate and bidentate-less teeth. In the embodiment, various strong dynamic supermolecular actions are introduced into the polymer, so that the dilatancy of the material can be enriched, the low-temperature dilatancy is improved, the microscopic self-repair of the material is accelerated, and the tear resistance of the material is improved.

In another preferred embodiment of the present invention, the dilatant hybrid dynamic polymer comprises a metal-ligand effect of three or more teeth and hydrogen bonding effect of three or more teeth. In the embodiment, the polymer contains various weak dynamic supermolecular actions, so that abundant dynamic and stimulus responsiveness can be obtained, the mechanical strength of the dilatant material is better enhanced, the shape memory function is conveniently realized together with common covalent crosslinking, and the functions of improving the toughness and the damage resistance of the material are promoted.

The non-hydrogen bond supermolecule function and the hydrogen bond function contained in the dilatant hybrid dynamic polymer can all play a role in crosslinking to form non-hydrogen bond supermolecule crosslinking and hydrogen bond crosslinking; it is also possible to carry out only polymerization, grafting, functionalization, etc. without crosslinking; it is also possible that the non-hydrogen bonding supermolecule acts as a crosslinking and the hydrogen bonding acts as polymerization, grafting, functionalization, etc.; it is also possible that the hydrogen bonding effect plays a role in crosslinking, but not the hydrogen bonding supermolecule effect only plays roles in polymerization, grafting, functionalization and the like; but the present invention is not limited thereto. In the embodiment of the invention, the non-hydrogen bond supermolecule function and the hydrogen bond function preferably play a role in crosslinking so as to improve the mechanical property, the dilatant property, the self-repairing property and the comprehensive energy absorption property of the material.

In the invention, the "hydrogen bond crosslinking" refers to a crosslinked structure formed by the joint participation of hydrogen bonding and common covalent bonds, and the degree of crosslinking of common covalent crosslinks in a crosslinked network is below the gel point (common covalent crosslinks do not exist in the crosslinked network), and the crosslinking formed by the hydrogen bonding is a necessary condition for forming the crosslinked network; based on the reversible characteristic of the hydrogen bond crosslinking, the formed crosslinked network can carry out dissociation-bonding balance of the crosslinked network under proper conditions, and the dynamic reversibility is shown. The crosslinked network formed by hydrogen bond crosslinking is the hydrogen bond crosslinked network. It should be noted that when two or more hydrogen bonding actions are contained in the hydrogen bonding crosslinked network and at least one of the hydrogen bonding actions is a weak dynamic hydrogen bonding action, it is regarded as a weak dynamic hydrogen bonding crosslinked network; when the hydrogen bond crosslinked network contains two or more hydrogen bonds and all the hydrogen bonds are strong dynamic hydrogen bonds, the hydrogen bond crosslinked network is regarded as the strong dynamic hydrogen bond crosslinked network.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

The single network structure can be a common covalent cross-linked network or a hybridization cross-linked network, and the cross-linking degree of the common covalent cross-linking is above the gel point; in the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms having at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a hybrid cross-linked network and a non-covalent cross-linked network, a combination of two hybrid cross-linked networks.

The dilatant hybrid dynamic polymer with a single network structure or a multi-network structure contains at least one vitrified dilatant polymer component so as to obtain vitrified dilatant. In addition, the dilatant hybrid dynamic polymer can also optionally contain dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure so as to enrich dilatant of dilatant polymer.

The non-crosslinked structure can be dispersed in the dilatant hybrid dynamic polymer with a single network structure or a multi-network structure, preferably the non-crosslinked dilatant polymer is selected, more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic non-hydrogen bond supermolecular effect and hydrogen bond effect, so that the extra dynamic dilatant can be conveniently obtained, the viscous flow of the chain segment is convenient, and the energy absorption performance is further improved.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has the advantages that the energy absorbing mechanism is very rich, besides the traditional energy absorbing mechanism, the energy absorbing method also comprises the dynamic reversible transformation process of energy absorbing through the dilatancy of the polymer, through the non-hydrogen bond supermolecular action and the hydrogen bond action contained in the polymer, and the energy absorbing method can be used as a sacrificial bond to absorb energy, and the like, so that excellent energy absorbing performance can be provided for the polymer energy absorbing material, and effective energy absorbing and impact resisting protection can be performed, thereby solving the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material, and embodying the novelty and creativity of the invention. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

The invention also relates toAnd a dilatant hybrid dynamic polymer, characterized in that it comprises at least a vitrified dilatant and comprises a common covalent cross-link above the gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action, wherein the hydrogen bond action is selected from hydrogen bond action of two teeth and teeth below, and hydrogen bond groups used for forming the hydrogen bond action of the teeth below are selected from at least one of the following structural components:

wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking and the hydrogen bonding effect above the gel point are simultaneously introduced to obtain the vitrification dilatancy and the optionally dynamic dilatancy; wherein the hydrogen bonding is selected from the hydrogen bonding of the number of teeth below two teeth, and the hydrogen bonding group used for forming the hydrogen bonding of the number of teeth below two teeth is selected from at least one of the following structural components:

Wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The invention also relates to an energy absorbing method based on the dilatant hybrid dynamic polymer, which is characterized in that the dilatant hybrid dynamic polymer is used as an energy absorbing material for energy absorbing application, and the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains coagulationOrdinary covalent cross-linking above the glue sites; the dilatant hybrid dynamic polymer also contains hydrogen bond action, wherein the hydrogen bond action is selected from hydrogen bond action of two teeth and teeth below, and hydrogen bond groups used for forming the hydrogen bond action of the teeth below are selected from at least one of the following structural components:

wherein (1)>

Representing a linkage to a polymer chain or any other suitable group/atom.

The dynamic units contained in the dilatant hybrid dynamic polymer are hydrogen bonding effects of the two teeth and the teeth below the two teeth, namely the dilatant hybrid dynamic polymer does not contain the dynamic units except the hydrogen bonding effects of the teeth below the two teeth. In the embodiment of the present invention, the hydrogen bond group for forming the hydrogen bond action of the number of teeth of the two teeth or less may be present only on the polymer chain skeleton, only on the polymer chain side group, only on the polymer chain skeleton/end group of the small molecule, or may be present simultaneously on at least two of the polymer chain skeleton, the side group and the end group. The hydrogen bonding action of the two teeth and the teeth below the two teeth has strong dynamic property, and can provide dynamic dilatancy for the polymer and rapid microcosmic self-repairing of material damage.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

The single network structure can be a common covalent cross-linked network or a hybridization cross-linked network, and the cross-linking degree of the common covalent cross-linking is above the gel point; in the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms having at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a hybrid cross-linked network and a hydrogen bonding cross-linked network, a combination of two hybrid cross-linked networks.

The dilatant hybrid dynamic polymer with a single network structure or a multi-network structure contains at least one vitrified dilatant polymer component so as to obtain vitrified dilatant. In addition, the dilatant hybrid dynamic polymer can also optionally contain dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure so as to enrich dilatant of dilatant polymer.

The non-crosslinked structure can be dispersed in the dilatant hybrid dynamic polymer with a single network structure or a multi-network structure, preferably the non-crosslinked dilatant polymer is selected, more preferably the non-crosslinked dilatant polymer contains at least one of the two teeth and the teeth below the two teeth for hydrogen bonding, so that the extra dynamic dilatant can be conveniently obtained, the viscous flow of the chain segment is facilitated, and the energy absorbing performance is further improved.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has the advantages that the energy absorbing mechanism is very rich, besides the traditional energy absorbing mechanism, the energy absorbing method also comprises the steps of energy absorption through the dilatancy of the polymer, dynamic reversible transformation through the hydrogen bond action contained in the polymer, and the like, and can be used as a sacrificial bond for energy absorption, so that the excellent energy absorbing performance can be provided for the polymer energy absorbing material, and effective impact resistance protection can be performed, and the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material can be solved. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

The invention also relates to a dilatant hybrid dynamic polymer which is characterized by at least containing vitrification dilatant and ordinary covalent cross-linking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action of the number of teeth above three teeth.

The invention also relates to a method for realizing the dilatancy of the hybrid dynamic polymer, which is characterized in that the vitrification dilatancy polymer component is introduced into the hybrid dynamic polymer, and the ordinary covalent crosslinking above the gel point and the hydrogen bonding effect of the teeth number above the tridentate are introduced at the same time, so that the vitrification dilatancy and the dynamic dilatancy are obtained.

The invention also relates to an energy absorption method based on the dilatant hybrid dynamic polymer, which is characterized in that the energy absorption method is carried out by taking the dilatant hybrid dynamic polymer as an energy absorption material, wherein the dilatant hybrid dynamic polymer at least contains vitrification dilatant and contains common covalent crosslinking above a gel point; the dilatant hybrid dynamic polymer also contains hydrogen bond action of the number of teeth above three teeth.

The three-tooth and more than three-tooth number hydrogen bonding action has weak dynamic property, not only provides weak dynamic property and microcosmic self-repairing property of material damage for the polymer, but also can be used as a sacrificial bond for energy absorption, toughness and damage resistance improvement; the crosslinking degree of hydrogen bond crosslinking formed by the hydrogen bond action can be reasonably regulated, the shape memory function of the dilatant material can be endowed, and the application range of the material is further widened.

In the embodiment of the present invention, the hydrogen bond group for forming the hydrogen bond action with the number of teeth of three or more teeth may be present only on the polymer chain skeleton, only on the polymer chain side group, only on the polymer chain skeleton/end group of the small molecule, or may be present simultaneously on at least two of the polymer chain skeleton, the side group and the end group.

By way of example, the hydrogen bonding groups for forming the hydrogen bonding action of the tridentate or more tooth number described in the present invention may be exemplified by the following hydrogen bonding groups, but the present invention is not limited thereto:

wherein, the liquid crystal display device comprises a liquid crystal display device,

representing a linkage to a polymer chain or any other suitable group/atom.

The dilatant hybrid dynamic polymer contains hydrogen bond action of the number of teeth of two teeth and below two teeth in addition to the hydrogen bond action of the number of teeth of three teeth and above three teeth so as to enrich non-covalent dynamic property of the material and obtain dynamic dilatant property. In the embodiment of the invention, the combination of the hydrogen bonding action of the three teeth and more teeth and the hydrogen bonding action of the two teeth and less teeth can better balance the mechanical property, the dynamic dilatancy, the microscopic self-repairing property and the like of the material.

The dilatant hybrid dynamic polymer can be in a single-network structure or a multi-network structure. It should be noted that, the degree of crosslinking of the ordinary covalent crosslinking in at least one crosslinked network in the dilatant hybrid dynamic polymer is above the gel point, so as to provide continuous structural support and mechanical properties, and avoid the problem that the dynamic strength of the dynamic unit contained in the dilatant hybrid dynamic polymer is rapidly reduced or even disintegrated in the dynamic reversible transformation process.

The single network structure can be a common covalent cross-linked network or a hybridization cross-linked network, and the cross-linking degree of the common covalent cross-linking is above the gel point; in the multi-network structure, the crosslinking degree of common covalent crosslinking in at least one crosslinking network is above the gel point, and the crosslinking forms of the rest crosslinking networks can be reasonably designed and regulated according to the requirement of the service performance. By way of example, the combination forms having at least two cross-linked networks described in the present invention include, but are not limited to, a combination of two common covalent cross-linked networks, a combination of a common covalent cross-linked network and a hybrid cross-linked network, a combination of a hybrid cross-linked network and a hydrogen bonding cross-linked network, a combination of two hybrid cross-linked networks.

The dilatant hybrid dynamic polymer with a single network structure or a multi-network structure contains at least one vitrified dilatant polymer component so as to obtain vitrified dilatant. In addition, the dilatant hybrid dynamic polymer can also optionally contain dynamic dilatant based on dynamic dilatant polymer components, entanglement dilatant based on entanglement dilatant polymer components, dispersive dilatant based on dispersive dilatant composition and aerodynamic dilatant based on aerodynamic dilatant structure so as to enrich dilatant of dilatant polymer.

The non-crosslinked structure can be dispersed in the dilatant hybrid dynamic polymer with a single network structure or a multi-network structure, preferably the non-crosslinked dilatant polymer is selected, more preferably the non-crosslinked dilatant polymer contains at least one of the two teeth and the teeth below the two teeth for hydrogen bonding, so that the extra dynamic dilatant can be conveniently obtained, the viscous flow of the chain segment is facilitated, and the energy absorbing performance is further improved.

Compared with the traditional polymer energy absorbing material and the energy absorbing method thereof, the energy absorbing method has the advantages that the energy absorbing mechanism is very rich, besides the traditional energy absorbing mechanism, the energy absorbing method also comprises the steps of energy absorption through the dilatancy of the polymer, dynamic reversible transformation through the hydrogen bond action contained in the polymer, and the like, and can be used as a sacrificial bond for energy absorption, so that the excellent energy absorbing performance can be provided for the polymer energy absorbing material, and effective impact resistance protection can be performed, and the problems of single energy absorbing mechanism, poor energy absorbing effect and the like of the traditional energy absorbing material can be solved. When energy is absorbed through the dilatancy of the polymer, different energy absorbing effects can be shown at different temperatures by regulating and controlling the vitrification dilatancy of the polymer, and the energy absorbing effects of the material at room temperature and low temperature are improved by dynamic dilatancy, entanglement dilatancy, dispersive dilatancy and aerodynamic dilatancy.

In embodiments of the invention, the component used to attach the dynamic unit may be a small molecule linker and/or a polymer segment. Wherein, the small molecule connecting group refers to a small molecule hydrocarbon group with molecular weight not more than 1000Da, which generally contains 1 to 71 carbon atoms, and can contain heteroatom groups or can not contain heteroatom groups. In general terms, the small molecule hydrocarbyl group may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, hybrid forms of any one, and combinations thereof: c (C) _1-71 Alkyl, ring C _3-71 Alkyl, phenyl, benzyl, aromatic hydrocarbon; wherein the small molecule hydrocarbon group can be selected from liquid crystal chain segments. The polymer chain segment comprises, but is not limited to, a polymer chain segment with a main chain of a carbon chain structure, a carbon hybrid chain structure, a carbon element chain structure, an element hybrid chain structure and a carbon hybrid element chain structure. The carbon chain structure is a structure with a main chain skeleton containing only carbon atoms; the carbon hetero-chain structure is a structure with a main chain skeleton containing carbon atoms and any one or more hetero atoms, wherein the hetero atoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure with a main chain skeleton containing 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 hetero-chain structure is a structure with a main chain skeleton and at least one hetero atom and at least one element atom; the carbon-hetero element chain structure is a main chain framework and simultaneously comprises carbon Structure of atoms, heteroatoms, and elemental atoms.

In one embodiment of the present invention, the polymer segment is preferably a polymer segment having a main chain of a carbon chain structure and a carbon hybrid chain structure, and is rich in structure and excellent in performance. By way of example, preferred carbon chain and carbon hybrid chain polymer segments include, but are not limited to, homopolymers, copolymers, modifications, derivatives, and the like such as acrylic polymers, saturated olefinic polymers, unsaturated olefinic polymers, polystyrene polymers, halogen-containing olefinic polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, poly (2-oxazoline) polymers, polyether polymers, polyester polymers, biopolyester polymers, polycarbonate polymers, polyurethane polymers, polyurea polymers, polyamide polymers, polyamine polymers, liquid crystal polymers, epoxy polymers, polythioether polymers, and the like.

In another embodiment of the present invention, the polymer chain segment is preferably in an element hetero-chain structure, for example, various polysilicone polymers, and the polymers generally have the characteristics of good corrosion resistance, oil resistance, water resistance, high and low temperature resistance, good tensile toughness, and the like.

In the present invention, the glass transition temperature of the dilatant hybrid dynamic polymer can be controlled at least by the rational design and selection of the connecting segments of the dynamic units (i.e. the small molecule linker and/or the polymer segments), but the present invention is not limited thereto.

In embodiments of the present invention, the small molecule and/or polymer segments used to attach the dynamic units may have any suitable topology, including but not limited to straight chain structures, branched structures (including but not limited to star, H-shaped, dendritic, comb, hyperbranched), cyclic structures (including but not limited to single ring, multiple ring, bridged ring, grommet, torus), two/three dimensional cluster structures, and combinations of two or more thereof; among them, a linear structure facilitating synthesis and control of the structure, a branched structure rich in structure, and a two-dimensional/three-dimensional cluster structure that can be locally enhanced are preferable, and a linear structure and a branched structure are more preferable. In the present invention, it is not even excluded to use crosslinked polymer particles for further polymerization/crosslinking reactions and linkages.

The above polymers and chain segments thereof selected in the invention can be directly selected from commercial raw materials, and can also be polymerized by a proper polymerization method.

The term "molecular weight" as used herein refers to the relative molecular mass of a substance, and for small molecular compounds, small molecular groups, and certain macromolecular compounds, macromolecular groups having a fixed structure, the molecular weight is generally monodisperse, i.e., has a fixed molecular weight; in the case of oligomers, polymers, oligomer residues, polymer residues, and the like having a polydispersity molecular weight, the molecular weight generally refers to the average molecular weight. Wherein, the small molecular compound and the small molecular group in the invention refer to a compound or a group with the molecular weight not more than 1000 Da; macromolecular compounds, macromolecular groups refer in particular to compounds or groups having a molecular weight of greater than 1000 Da.

The term "heteroatom" as used herein refers to a common non-carbon atom such as nitrogen, oxygen, sulfur, phosphorus, silicon, boron, and the like.

The "heteroatom-containing linking group" as described herein may be any suitable heteroatom-containing linking group which may be selected from any one or a combination of any of the following: ether group, thio group, thioether group, divalent tertiary amine group, trivalent tertiary amine group, divalent silicon group, trivalent silicon group, tetravalent silicon group, divalent phosphorus group, trivalent phosphorus group, divalent boron group, trivalent boron group.

"hydrocarbyl" as referred to in the present invention includes aliphatic hydrocarbyl groups (simply referred to as "aliphatic hydrocarbyl groups") and aromatic hydrocarbyl groups (simply referred to as "aromatic hydrocarbyl groups"); the alkyl group may be a saturated or unsaturated alkyl group; the topology of the hydrocarbon group may be a straight chain structure, a branched structure, and a cyclic structure; the term "alkyl" refers to a saturated form of aliphatic hydrocarbon group; the "heterohydrocarbyl" refers to a hydrocarbyl group formed by substituting a part of carbon atoms in the hydrocarbyl group with heteroatoms; the term "substituted hydrocarbon group" meansIs a hydrocarbon group formed by substitution of some or all of the hydrogen atoms in the hydrocarbon group with halogen atoms, heteroatoms or any other suitable substituent. In the present invention, reference to "hydrocarbyl" includes hydrocarbyl in any of its isomeric forms, e.g., the propyl group includes, but is not limited to, n-propyl, isopropyl. In the present invention, the subscript position of C is marked with the lower label of the range of the number of carbon atoms in the group, which means that the group has the range of the number of carbon atoms, such as C ₁₀ Means "having 10 carbon atoms", C _1-10 Meaning "having from 1 to 10 carbon atoms", when a group may be selected from C _1-10 When the hydrocarbon group is selected from any hydrocarbon group having carbon atoms in the range indicated by the subscript, it may be selected from C ₁ 、C ₂ 、C ₃ 、C ₄ 、C ₅ 、C ₆ 、C ₇ 、C ₈ 、C ₉ 、C ₁₀ Any one of the hydrocarbon groups.

In the present invention, one or more phase change additives may also be added as needed in the preparation of the dilatant hybrid dynamic polymer, especially in the preparation of dilatant polymer foams with slow resilience.

In the invention, when preparing the dilatant hybrid dynamic polymer, auxiliary agents, fillers and swelling agents can be selectively added or used as the formula components of the polymer according to the actual requirements of the preparation process, the molding process, the use performance requirements and the like, so that the processing performance of the material can be improved, the quality and the yield of the product can be improved, the cost of the product can be reduced, or certain special application performance can be provided for the product, but the additives or the use matters are not required.

Wherein the auxiliary agent can include, but is not limited to, one or a combination of several of the following, such as synthesis auxiliary agent, including catalyst and initiator; stabilization aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; auxiliary agents for improving mechanical properties, including toughening agents, coupling agents and compatibilizers; auxiliary agents for improving the processing performance, including solvents, lubricants, release agents, plasticizers, thickeners, thixotropic agents and leveling agents; auxiliary agents for changing the color light, including colorants, fluorescent whitening agents, matting agents; other adjuvants including phase change additives, antistatic agents, sterilizing and mildew preventing agents, foaming agents, foam stabilizers, nucleating agents, rheology agents, and the like.

Wherein the compatilizer can improve interfacial properties between polymer samples or between the compatilizer and inorganic filler or reinforcing material by means of intermolecular bonding force, promote incompatible polymers or inorganic materials to be combined together, further obtain stable blend, reduce viscosity of material melt in the plastic processing process, improve dispersity of the filler to improve processing performance, further obtain good surface quality and mechanical, thermal and electrical properties of the product, and comprises any one or any of the following compatilizer: coupling agent type compatibilizers including chromium organic acid complexes, silane coupling agents, titanate coupling agents, sulfonyl azide coupling agents, aluminate coupling agents, zirconate coupling agents, and the like, such as divinyl tetramethyl disiloxane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tris (β -methoxyethoxy) silane, γ -glycidylpropyl-trimethoxysilane, γ -methacryloxypropyl-trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl-methyl-trimethoxysilane, γ -aminopropyl triethoxysilane, γ - (2, 3-glycidoxypropyl) propyl trimethoxysilane, γ -chloropropyl-trimethoxysilane, γ -mercaptopropyl-trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl-trimethoxysilane; copolymer type compatibilizers including block copolymers, graft copolymers and random copolymers such as polyethylene glycol-polydimethylsiloxane copolymers, polyethylene-polystyrene copolymers, polypropylene-polystyrene copolymers, ABS-maleic anhydride copolymers, polyethylene-maleic anhydride copolymers, polypropylene-maleic anhydride copolymers, and the like; surfactant-type compatibilizers, which include anionic surfactants such as stearic acid, sodium dodecylbenzenesulfonate, etc., cationic surfactants such as quaternary ammonium compounds, etc., nonionic surfactants such as alkyl glucosides (APG), polyglycidyl esters, fatty acid glycerides, fatty acid sorbitan (span), polysorbate (tween), etc., amphoteric surfactants such as lecithin, amino acid type, betaine type, etc., and further include built surfactants, other surfactants, etc. Among them, preferable examples of the compatibilizing agent include γ -aminopropyl triethoxysilane (silane coupling agent KH 550), γ - (2, 3-epoxypropoxy) propyl trimethoxysilane (silane coupling agent KH 560), polyethylene glycol-polydimethylsiloxane copolymer, polyethylene-maleic anhydride copolymer, polypropylene-maleic anhydride copolymer, stearic acid, sodium dodecylbenzenesulfonate, and glyceryl monostearate. The amount of the compatibilizing agent to be used is not particularly limited and is generally 0.5 to 2% by weight.

The phase change additive can absorb heat, improves the comfort of the dilatant material in the use process, and can prevent the mechanical strength and the support stability of the foam material from being influenced by overhigh temperature. The phase change additive refers to a substance with higher heat of fusion, which melts and solidifies at a certain temperature, and absorbs heat from the environment or emits heat to the environment through the phase change process, thereby realizing the process of storing and releasing heat energy. The phase change additives include, but are not limited to: salt hydrate phase-change material, organic phase-change material and inorganic salt phase-change material. By way of example, the salt hydrate phase change material may be selected from, but is not limited to: sodium sulfate hydrate (Na) ₂ SO ₄ ·10H ₂ O), sodium acetate trihydrate (NaCH) ₃ COO·3H ₂ O), aqueous salts of calcium chloride (CaCl) ₂ ·6H ₂ O), sodium dihydrogen phosphate dodecahydrate salt (NaHPO) ₄ ·12H ₂ O), sodium carbonate hydrate (Na ₂ CO ₃ ·12H ₂ O), magnesium nitrate hydrate salt (Mg (NO) ₃ ) ₂ ·6H ₂ O), calcium nitrate hydrate salt (Ca (NO) ₃ ) ₂ ·4H ₂ O); the organic phase change material may be selected from, but is not limited to: paraffin, azobenzene (e.g.

/>

) Fatty acids (e.g. straight-chain C) _10-25 Fatty acids), fatty alcohols (e.g. straight chain C _10-25 Fatty alcohols), polyols (e.g., pentaerythritol, 2-dimethylol propanol, neopentyl glycol), sugar alcohols (e.g., inositol, D-mannitol, galactitol), polyethylene glycols, crosslinked polyolefins (e.g., polyethylene), crosslinked polyacetals, cellulose graft copolymers, polyester graft copolymers, polystyrene graft copolymers, silane graft copolymers; the inorganic salt phase change material may be selected from, but is not limited to: layered perovskite, KHF ₂ 、NH ₄ SCN。

In the present invention, the filler includes, but is not limited to, inorganic nonmetallic fillers, metallic fillers, organic fillers, organometallic compound fillers.

The inorganic nonmetallic fillers include, but are not limited to, any one or any several of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon black, quartz, mica powder, clay, asbestos fibers, orthofeldspar, chalk, limestone, barite powder, gypsum, silica, graphite, carbon black, graphene oxide, graphene, carbon nanotubes, black phosphorus nanoplatelets, molybdenum disulfide, diatomaceous earth, red mud, wollastonite, silica-alumina carbon black, aluminum hydroxide, magnesium hydroxide, nano-Fe ₃ O ₄ Particle, nano gamma-Fe ₂ O ₃ Particle, nano MgFe ₂ O ₄ Granular, nano MnFe ₂ O ₄ Particulate, nano CoFe ₂ O ₄ Particles, 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), upconverting crystal particles (including but not limited to NaYF ₄ :Er、CaF ₂ :Er、Gd ₂ (MoO ₄ ) ₃ :Er、Y ₂ O ₃ :Er、Gd ₂ O ₂ S:Er、BaY ₂ F ₈ :Er、LiNbO ₃ :Er,Yb,Ln、Gd ₂ O ₂ :Er,Yb、Y ₃ Al ₅ O ₁₂ :Er,Yb、TiO ₂ :Er,Yb、YF ₃ :Er,Yb、Lu ₂ O ₃ :Yb,Tm、NaYF ₄ :Er,Yb、LaCl ₃ :Pr、NaGdF ₄ :Yb,Tm@NaGdF ₄ Core-shell nanostructure of Ln, naYF ₄ :Yb,Tm、Y2BaZnO ₅ :Yb,Ho、NaYF ₄ :Yb,Er@NaYF ₄ Core-shell nanostructure of Yb, tm, naYF ₄ :Yb,Tm@NaGdF ₄ Core-shell nano-structure 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 nonmetallic fillers with conductivity are preferred, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, to facilitate obtaining a composite material that is conductive and/or has electrothermal functionality. In another embodiment of the present invention, nonmetallic fillers with heat generating function under the action of infrared and/or near infrared light are preferred, including but not limited to graphene, graphene oxide, carbon nanotubes, black phosphorus nanoplatelets, nano Fe ₃ O ₄ It is convenient to obtain a composite material that can be heated with infrared and/or near infrared light. In another embodiment of the present invention, inorganic nonmetallic fillers with thermal conductivity are preferred, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, to facilitate obtaining a composite material with thermal conductivity.

The metal filler comprises a metal compound, 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-CoPt ₃ Particles, nano FePt particles, nano FePd particles, ferronickel bimetallic magnetic nano particles and other nano gold capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic effectsParticles 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 subjected to electromagnetic and/or near infrared heating, including but not limited to nanogold, nanosilver, or nanosilver, are preferred for remote sensing heating. In another embodiment of the present invention, a liquid metal filler is preferred to enhance the thermal and electrical conductivity properties of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler includes, but is not limited to, any one or any several of the following: (1) natural organic fillers; (2) a synthetic resin filler; (3) a synthetic rubber filler; (4) a synthetic fibrous filler; (5) conjugated polymer; (6) organic functional dyes/pigments. The organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal and the like has important significance for the invention, and the properties of the organic filler can be fully utilized to obtain the versatility.

The organic metal compound filler contains metal organic complex components, wherein metal atoms and carbon atoms are directly connected into bonds (including coordination bonds, sigma bonds and the like), can be small molecules or large molecules, and can be amorphous or crystalline in structure. The metal organic compound has excellent performance including ultraviolet absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat and other performances.

Wherein the filler type is not limited, and is mainly determined according to the required material performance, preferably calcium carbonate, clay, carbon black, graphene, (hollow) glass beads and nano Fe ₃ O ₄ Particles, nano silicon dioxide, quantum dots, up-conversion metal particles, glass fibers, carbon fibers, metal powder, nano metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organic metal compounds and organic materials with photo-thermal properties. The amount of filler used is not particularly limited and is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be optionally modified and then dispersed and compounded or directly connected into the polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, especially for photo-thermal, Has important significance in electromagnetic heat and other actions.

Wherein the swelling agent can include, but is not limited to, water, organic solvents, ionic liquids, oligomers, plasticizers. Among them, oligomers can also be considered as plasticizers.

Wherein the ionic liquid in the swelling agent generally consists of organic cations and inorganic anions, and the cations are selected from the group consisting of, by way of example, alkyl quaternary ammonium ions, alkyl Ji ions, 1, 3-dialkyl substituted imidazole ions, N-alkyl substituted pyridine ions and the like; the anions are selected from the group consisting of but not limited to halogen ions, tetrafluoroborate ions, hexafluorophosphate ions, and CF ₃ SO ₃ ^- 、(CF3SO ₂ ) ₂ N ^- 、C ₃ F ₇ COO ^- 、C ₄ F ₉ SO ₃ ^- 、CF ₃ COO ^- 、(CF ₃ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₂ N ^- 、SbF ₆ ^- 、AsF ₆ ^- Etc. In the ionic liquid used in the invention, the cation is preferably imidazole cation, and the anion is preferably hexafluorophosphate ion and tetrafluoroborate ion.

In embodiments of the present invention, the dilatant hybrid dynamic polymer may be in the form of a gel (including hydrogels, organogels, oligomer-swollen gels, plasticizer-swollen gels, ionic liquid-swollen gels), elastomer, foam, etc., wherein the foam typically contains no more than 10wt% of the soluble small molecular weight component and no less than 50wt% of the small molecular weight component. The elastomer has relatively fixed shape and volume, relatively good mechanical strength, no restriction of organic swelling agent or water, relatively good elasticity, toughness, damping buffering and other characteristics, and is suitable for preparing energy absorbing materials. The gel has higher softness and lower solid content, the swelling agent has the functions of conduction, transportation and the like, has good stability, mechanical strength and damping and buffering characteristics, and is suitable for preparing energy absorbing materials. The foam material has the advantages of low density, portability and high specific strength, can overcome the problem of low mechanical strength of partial organogel, and has the characteristics of good elasticity, softness and comfort. In addition, the foam material has the capability of absorbing impact load, is convenient to obtain excellent energy absorption and protection effects, and is very suitable for preparing the buffering and damping material. Materials of different morphologies may have suitable uses in different fields.

In an embodiment of the present invention, the polymer gel may be obtained by reacting in a swelling agent (including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof), or may be obtained by swelling with a swelling agent after the polymer is prepared. Of course, the present invention is not limited thereto and those skilled in the art can implement the logic and context of the present invention reasonably efficiently.

In the preparation process of the polymer, three methods of a mechanical foaming method, a physical foaming method and a chemical foaming method are mainly adopted for foaming.

Wherein, the mechanical foaming method is to introduce a large amount of air or other gases into emulsion, suspension or solution of the polymer by strong stirring in the preparation process of the polymer to form a uniform foam body, and then to form the foam material by physical or chemical change. Air may be introduced and emulsifiers or surfactants may be added to shorten the molding cycle.

Wherein, the physical foaming method realizes the foaming of the polymer by utilizing the physical principle in the preparation process of the polymer, and comprises but is not limited to the following methods: (1) Inert gas foaming, namely, pressing inert gas into molten polymer or pasty material under the condition of pressurization, and then decompressing and heating to expand and foam the dissolved gas; (2) Evaporating, gasifying and foaming by utilizing low-boiling point liquid, namely pressing the low-boiling point liquid into a polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, and then heating and softening the polymer, so that the liquid is evaporated, gasified and foamed; (3) The dissolution method is to immerse the polymer with liquid medium to dissolve the solid matter added in advance, so that a large amount of pores appear in the polymer to form foaming, for example, the soluble matter salt is firstly mixed with the polymer, after the product is formed, the product is put in water for repeated treatment, and the soluble matter is dissolved out to obtain the open-cell foam product; (4) Hollow microsphere method, namely adding hollow microspheres into the material, and then compounding to form closed cell foam polymer; (5) A method of filling expandable particles, comprising mixing expandable particles and expanding the expandable particles during molding or mixing to actively expand the polymer material; among them, foaming is preferably carried out by a method of dissolving an inert gas and a low boiling point liquid in a polymer. The physical foaming method has the advantages of low toxicity in operation, low foaming raw material cost, no residual foaming agent and the like. In addition, the preparation can also be carried out by a freeze-drying method.

Wherein, the chemical foaming method is a method for generating gas along with chemical reaction in the polymer foaming process, and comprises but is not limited to the following two methods: (1) The thermal decomposition type foaming agent foaming method is to foam the gas decomposed and released after heating by using a chemical foaming agent. (2) Foaming processes in which interactions between polymer components produce a gas, i.e., the foaming process in which a chemical reaction between two or more components in a foaming system is used to produce an inert gas (e.g., carbon dioxide or nitrogen) to expand the polymer. In the foaming process, in order to control the balance of polymerization reaction and foaming reaction, a small amount of catalyst and foam stabilizer (or surfactant) are generally added to ensure good quality of the product. Among them, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

In the preparation of the polymer, a person skilled in the art can select a proper foaming method and a foam molding method to prepare the foam according to the actual preparation condition and the target polymer property.

In an embodiment of the present invention, the structure of the polymer foam material relates to three of an open cell structure, a closed cell structure, and a half-open and half-closed structure. In the open pore structure, the cells are mutually communicated or completely communicated, and the single dimension or three dimensions can pass through gas or liquid, and the pore diameter of the cells is 0.01-3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from the cells by wall membranes, most of the cells are not mutually communicated, and the pore diameters of the cells are 0.01-3 mm. The contained foam holes are of semi-open structures with structures which are not communicated with each other. For the foam structure which has formed closed cells, it can also be made into an open cell structure by mechanical pressure or chemical method, and the person skilled in the art can choose according to the actual need.

In embodiments of the present invention, polymer foams are classified by their hardness into three categories, soft, hard and semi-hard: (1) A flexible foam having an elastic modulus of less than 70MPa at 23 ℃ and 50% relative humidity; (2) Rigid foam having an elastic modulus greater than 700MPa at 23 ℃ and 50% relative humidity; (3) Semi-rigid (or semi-flexible) foams, foams between the two classes, have an elastic modulus between 70MPa and 700 MPa.

In embodiments of the present invention, polymer foams can be further classified into low foaming, medium foaming and high foaming according to their density. Low foaming foam material having a density greater than 0.4g/cm ³ The foaming multiplying power is less than 1.5; a density of 0.1 to 0.4g/cm ³ The foaming multiplying power is 1.5-9; while the high foaming foam material has a density of less than 0.1g/cm ³ The foaming ratio is more than 9.

Those skilled in the art can select a suitable foaming method and molding method to prepare the polymer foam product according to actual conditions and requirements.

In the invention, the method for preparing the dilatant hybrid dynamic polymer can reasonably select and regulate according to the differences of the composition components, the contained dilatant components/structures, the crosslinked network structure, the polymer state, the using functions and the like of the dilatant hybrid dynamic polymer. The content, proportion, etc. of the polymer/reaction raw materials (such as vitrified dilatant polymer, dynamic dilatant polymer, entanglement dilatant polymer, non-dilatant small molecule/oligomer, cross-linking agent, chain extender, etc.), catalyst, initiator, pore opening agent, compatilizer, foaming agent, vulcanizing agent and other auxiliary agents, fillers, etc. involved in the preparation process can be reasonably regulated according to the polymerization/reaction mechanism, polymerization/reaction activity, desired dilatant performance and other functionalities.

In the invention, a one-step method can be adopted to prepare the dilatant hybrid dynamic polymer, namely, the dilatant hybrid dynamic polymer is formed in situ in the reaction process of preparing vitrified dilatant polymer components, dynamic dilatant polymer components, entanglement dilatant polymer components and aerodynamic dilatant structures from non-dilatant components such as micromolecule monomers, oligomers and the like containing active groups; it is also possible to prepare the dilatant hybrid dynamic polymer by a multistage process, i.e. to prepare the vitrified dilatant polymer, the dynamic dilatant polymer and the entanglement dilatant polymer in advance and then to further react with other reactive materials, such as cross-linking agents, etc., by means of mutual reaction of reactive groups contained therein, or to physically blend the vitrified dilatant polymer, the dynamic dilatant polymer and the entanglement dilatant polymer, and the dispersion dilatant composition to obtain the dilatant hybrid dynamic polymer.

The invention relates to a preparation method of a dilatant hybrid dynamic polymer, wherein the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, and is prepared by a one-step method through a chemical hybridization process. The method comprises the steps of premixing a vitrified dilatant polymer or a raw material thereof, a dynamic dilatant polymer or a raw material thereof, and optionally other auxiliary agents and optional fillers, filling the mixture into a proper mold, and carrying out reaction molding under certain temperature and pressure conditions to obtain the dilatant hybrid dynamic polymer. Wherein, the mass ratio of the vitrification dilatant polymer or the raw materials thereof to the dynamic dilatant polymer or the raw materials thereof is 1:0.05-9, preferably 1:0.05-5, more preferably 1:0.3-1.5; when present, the preferred weight ratio of other adjuvants to the polymer matrix is from 0.1 to 40wt%, more preferably from 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%. The preparation method is suitable for preparing the dilatant hybrid dynamic polymer which is used in a single network structure and is blended with the non-crosslinked dilatant polymer in the network, and the dilatant of the polymer can be regulated and controlled by regulating and controlling the content and the proportion of raw material components with vitrification dilatant and dynamic dilatant, so that the dilatant requirements of different application scenes on the dilatant of the material are met. For example, when the dilatant material is only required to be used at a very narrow temperature, the dynamic dilatant forming composition may be suitably reduced to achieve an increased dilatant sensitivity to temperature. On the contrary, when the dilatant material needs to be used in a wider temperature range, especially needs to be used at a low temperature, the forming component of dynamic dilatant can be properly increased so as to improve the low temperature resistance of the material, so that the dilatant material can keep stable dilatant at a low temperature even at a very low temperature and resist impact and absorb energy.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, wherein the dilatant hybrid dynamic polymer contains vitrified dilatant and dynamic dilatant, and is prepared by a one-step method through a chemical hybridization process. The preparation method comprises the steps of premixing a vitrified dilatant polymer or raw materials thereof, a strong dynamic covalent bond and/or a strong dynamic non-covalent effect, optional other auxiliary agents and optional fillers, filling the premixed vitrified dilatant polymer or raw materials thereof into a proper mold, and carrying out reaction molding under certain temperature and pressure conditions to obtain the dilatant hybrid dynamic polymer. Wherein, when other auxiliary agents are present, the preferred weight ratio of the other auxiliary agents to the polymer matrix is 0.1 to 40wt%, more preferably 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, wherein the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, and is prepared by adopting a physical blending process, and the preparation method comprises the following steps of: firstly preparing a crosslinked network containing vitrification dilatant and a dynamic dilatant polymer, and then physically blending the two crosslinked networks, optional other auxiliary agents and optional fillers, wherein the weight ratio of the vitrification dilatant polymer crosslinked network to the dynamic dilatant crosslinked network is 1:0.05 to 5, more preferably 1:0.3 to 2, more preferably 1:0.5 to 1.5; wherein, when other auxiliary agents are present, the preferred weight ratio of the other auxiliary agents to the polymer matrix is 0.1 to 40wt%, more preferably 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%. The other more preferable preparation method of the invention is to prepare one of the crosslinked networks, then swell the crosslinked network in the reaction raw material for preparing the other crosslinked network, and then polymerize/react to obtain the other crosslinked network, so as to realize the interpenetrating of the vitrification dilatant crosslinked network and the dynamic dilatant crosslinked network, provide vitrification dilatant and dynamic dilatant for the polymer, and obtain better mechanical strength and damage resistance.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, wherein the dilatant hybrid dynamic polymer contains vitrification dilatant and dynamic dilatant, and is prepared by adopting a physical blending process. The method comprises the following steps: firstly preparing a crosslinked network containing vitrification dilatancy and a non-crosslinked dynamic dilatancy polymer, and then physically blending the two polymers to obtain the polymer; among them, the preferable ratio of the crosslinked network of the vitrified dilatant polymer to the uncrosslinked dynamic dilatant polymer is 1:0.2 to 1.5, more preferably 1:0.4 to 1. In the preparation process, other auxiliary agents and fillers can be optionally added according to the application scene and the requirement of the service performance; wherein, when other auxiliary agents are present, the preferred weight ratio of the other auxiliary agents to the vitrified dilatant polymer cross-linked network is 0.1-40wt%, more preferably 0.5-20wt%; when present, the preferred weight ratio of filler to the vitreous dilatant polymer crosslinked network is from 0.1 to 30% by weight, more preferably from 2 to 20% by weight. The preparation method of the invention is that the non-crosslinked dynamic dilatant polymer is prepared firstly, and then the non-crosslinked dynamic dilatant polymer is blended and dispersed in the reaction liquid for preparing the vitrified dilatant crosslinked network, so that the dynamic dilatant polymer is more uniformly dispersed in the prepared vitrified dilatant crosslinked network, and the dilatant material has stable and uniform dilatant everywhere.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which comprises the steps of premixing the vitrified dilatant polymer or the raw materials thereof, the dynamic dilatant polymer or the raw materials thereof, and optional other auxiliary agents and optional fillers, filling the premixed dilatant polymer or the raw materials thereof into a proper mold, and carrying out hot press molding under certain temperature and pressure conditions to obtain the dilatant hybrid dynamic polymer. Wherein, the mass ratio of the vitrification dilatant polymer or the raw materials thereof to the dynamic dilatant polymer or the raw materials thereof is 1:0.05-9, preferably 1:0.05-5, more preferably 1:0.3-1.5. When present, the preferred weight ratio of other adjuvants to the polymer matrix is from 0.1 to 40wt%, more preferably from 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which comprises the steps of carrying out premixing processes such as open-milling/banburying and the like on a rubber matrix, a vulcanizing agent/cross-linking agent (comprising a dynamic cross-linking agent), a reinforcing agent (such as carbon black, graphene, carbon nano tubes, football, nano silicon dioxide, submicron silicon dioxide, nano calcium carbonate, nano montmorillonite, nano pottery clay, kaolin and the like), and optional other auxiliary agents and optional fillers, then filling the rubber matrix into a proper mold, and carrying out hot press molding under certain temperature and pressure conditions to obtain the dilatant hybrid dynamic polymer. Wherein the preferred weight ratio of vulcanizing agent/crosslinking agent to rubber matrix is 0.5-30wt%, more preferably 1.2-15wt%; the preferred weight ratio of reinforcing agent to rubber matrix is from 2 to 40wt%, more preferably from 5 to 20wt%. When present, the preferred weight ratio of other adjuvants to the rubber matrix is from 0.1 to 40wt%, more preferably from 0.5 to 20wt%; when present, the preferred weight ratio of filler to rubber matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%. The rubber matrix can be unmodified raw rubber or dynamic covalent crosslinking/non-covalent crosslinking/hybrid dynamic crosslinking modified rubber; the rubber matrix can be only one single rubber, or can be a plurality of rubbers and rubber and other polymer matrixes (such as EVA, polyvinyl chloride and the like); among them, various rubbers and blends of rubbers with other polymer matrices are preferably employed as the dilatant polymer matrix, which is capable of combining the inherent material properties of different matrices, and which is more conducive to regulating the dilatancy and other overall properties of the material. The rubber matrix includes, as examples, but is not limited to, silicone rubber, ethylene propylene diene rubber, natural rubber, isoprene rubber, styrene butadiene rubber, neoprene rubber, nitrile rubber, and fluororubber.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which comprises the steps of premixing the vitrified dilatant polymer or the raw materials thereof, the dynamic dilatant polymer or the raw materials thereof, the foaming agent, optional other auxiliary agents and optional fillers, filling the premixed dilatant polymer or the raw materials thereof into a proper mold, and carrying out hot press molding under certain temperature and pressure conditions to prepare the dilatant hybrid dynamic polymer; wherein, the mass ratio of the vitrification dilatant polymer or the raw materials thereof to the dynamic dilatant polymer or the raw materials thereof is 1:0.05-10, preferably 1:0.2 to 5, more preferably 1:0.3-1.5. Wherein the preferred weight ratio of blowing agent to polymer matrix is 0.1-40wt%, more preferably 1-20wt%; when present, the preferred weight ratio of other adjuvants to the polymer matrix is from 0.1 to 40wt%, more preferably from 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%. Wherein the blowing agent comprises a physical blowing agent such as carbon dioxide, nitrogen, argon, methane, ethane, propane, butane, isobutane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, toluene, methyl ether, ethyl ether, petroleum ether, methyl chloride, methylene chloride, ethylene dichloride, dichlorodifluoromethane, trifluoromethane, hydrochlorofluorocarbon-22, hydrochlorofluorocarbon-142 b, hydrofluorocarbon-134 a, hydrofluorocarbon-152 a, chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-114; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium ammonium carbonate, azide compounds, boron hydride compounds, and the like; organic blowing agents such as N, N '-dinitroso pentamethylene tetramine, N' -dimethyl-N, N '-dinitroso terephthalamide, azodicarbonamide, azodicarbonate diisopropyl azodicarbonate, azodicarbonamide potassium formate, azodiisobutyronitrile, 4' -oxybis-benzenesulfonyl hydrazide, 3 '-disulfonyl hydrazide diphenyl sulfone, 1, 3-benzodihuano hydrazide, benzenesulfonyl hydrazide, trihydrazino triazine, p-toluenesulfonyl semicarbazide, biphenyl-4, 4' -disulfonyl azide, diazo aminobenzene; physical microsphere/particle foaming agent, such as foamable microsphere produced by Ackersinobell and other companies, the foaming agent is preferably environment-friendly and harmless carbon dioxide, nitrogen and argon, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylene tetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitroso terephthalamide (foaming agent NTA) and physical microsphere foaming agent.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which is polyurethane foam and comprises the following preparation processes: dispersing a pre-prepared dynamic dilatant polymer in a polyol component of polyurethane to obtain a material A, adding an isocyanate component (material B) into the material A, and foaming to obtain a dilatant hybrid dynamic polymer blended with and dispersed with the dilatant polymer; wherein the component proportion of the material A is 5 to 100 parts by mass of polyether polyol, 0 to 45 parts by mass of modified polyether polyol, 0 to 50 parts by mass of polyester polyol, 5 to 200 parts by mass of dynamic dilatant polymer, 0.05 to 30 parts by mass of compatilizer, 0.1 to 20 parts by mass of foam stabilizer (such as organosilicon foam stabilizer), 0.1 to 20 parts by mass of catalyst, 0 to 15 parts by mass of pore opening agent, 0.1 to 15 parts by mass of foaming agent (such as deionized water) and other optional auxiliary agents and fillers; wherein the isocyanate index is from 0.8 to 1.3, preferably from 0.9 to 1.15; wherein, when other auxiliary agents are present, the preferred weight ratio of the other auxiliary agents to the polymer matrix is 0.1 to 40wt%, more preferably 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%; wherein the dynamic dilatant polymer is preferably an organosilicon polymer containing dynamic boron-containing covalent bonds (such as polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, homopolymers, copolymers, modifications and derivatives of hydrogen-containing polysiloxanes and the like), and saturated olefins or polyolefin unsaturated polyolefins containing dynamic boron-containing covalent bonds (such as ethylene-propylene copolymers, polyisobutylene, polychloroprene, poly cis-1, 4-isoprene, poly trans-1, 4-isoprene, styrene-butadiene copolymers and modifications and derivatives thereof), wherein the dynamic dilatant polymer can be in a non-crosslinked structure or can be a strong dynamic polymer crosslinked by the dynamic boron-containing covalent bonds; wherein the catalyst comprises an amine catalyst and an organometallic catalyst such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylaminoethyl) ethanol, trimethylhydroxyethyl-propylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N ' -trimethyl-N ' -hydroxyethyl-diamine ethyl ether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropyl hexanoic acid, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctanoate, lead, potassium oleate, zinc naphthenate, cobalt oleate, sodium naphthenate, potassium naphthenate, sodium benzoate, potassium benzoate, sodium benzoate, potassium benzoate, phenylcarboxylate, and the like.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which is polyurethane foam, and the preparation process comprises the following three steps: firstly, preparing a dynamic dilatant polymer and dispersing the dynamic dilatant polymer in a proper solvent to obtain a dynamic dilatant polymer solution with a certain concentration for standby, wherein the mass concentration of the dynamic dilatant polymer solution is preferably 0.01-5g/cm3, and preferably 0.1-0.5g/cm3; secondly, preparing polyurethane foam, which comprises the following steps: adding an isocyanate component (material B) into a polyol component (material A) to foam to obtain polyurethane foam, wherein the component proportion of the material A is 5-100 parts by mass of polyether polyol, 0-45 parts by mass of modified polyether polyol, 0-50 parts by mass of polyester polyol, 0.1-20 parts by mass of foam stabilizer (such as organic silicon foam stabilizer), 0.1-20 parts by mass of catalyst, 1-20 parts by mass of pore opening agent, 0.1-15 parts by mass of foaming agent (such as deionized water) and other optional auxiliary agents and fillers; wherein the isocyanate index is from 0.8 to 1.3, preferably from 0.9 to 1.15; wherein the open cell content of the foam is 1% -90%, more preferably 5% -60%, still more preferably 10% -45%; wherein, when other auxiliary agents are present, the preferred weight ratio of the other auxiliary agents to the polymer matrix is 0.1 to 40wt%, more preferably 0.5 to 20wt%; when present, the preferred weight ratio of filler to polymer matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%; and thirdly, dipping the prepared polyurethane foam into a dynamic dilatant polymer solution, and drying to remove the solvent to obtain the hybrid dynamic polymer containing the dynamic dilatant polymer, wherein the dynamic dilatant polymer can be promoted to enter foam holes of the foam and the filling rate is increased by stirring, heating, pressurizing, prolonging the dipping time and the like in the dipping process.

The invention also relates to a preparation method of the dilatant hybrid dynamic polymer, which comprises the steps of carrying out premixing processes such as open-loop/banburying and the like on a rubber matrix, a vulcanizing agent/cross-linking agent (containing the dynamic cross-linking agent), a reinforcing agent (such as carbon black, graphene, carbon nano tubes, football, nano silicon dioxide, submicron silicon dioxide, nano calcium carbonate, nano montmorillonite clay, nano pottery clay, kaolin and the like), a foaming agent, a foam stabilizer, and optional other auxiliary agents and optional fillers, filling the premixed processes into a proper mold, and carrying out hot-press foaming molding under certain temperature and pressure conditions to prepare the dilatant hybrid dynamic polymer foam. Wherein the preferred weight ratio of vulcanizing agent/crosslinking agent to rubber matrix is 0.5-30wt%, more preferably 1.2-15wt%; the preferred weight ratio of reinforcing agent to rubber matrix is 2-40wt%, more preferably 5-20wt%; the preferred weight ratio of reinforcing agent to rubber matrix is 2-40wt%, more preferably 5-20wt%; the preferred weight ratio of foaming agent to rubber matrix is 0.5-12wt%, more preferably 1.2-8wt%; the preferred weight ratio of foaming agent to rubber matrix is 0.1-40wt%, more preferably 1-20wt%; the preferred weight ratio of foam stabilizer to rubber matrix is 0-15wt%, more preferably 0.5-10wt%; when present, the preferred weight ratio of other adjuvants to the rubber matrix is from 0.1 to 40wt%, more preferably from 0.5 to 20wt%; when present, the preferred weight ratio of filler to rubber matrix is from 0.1 to 30wt%, more preferably from 2 to 20wt%. The rubber matrix can be unmodified raw rubber or dynamic covalent crosslinking/non-covalent crosslinking/hybrid dynamic crosslinking modified rubber; the rubber matrix can be only one single rubber, or can be a plurality of rubbers and rubber and other polymer matrixes (such as EVA, polyvinyl chloride and the like); among them, various rubbers and blends of rubbers with other polymer matrices are preferably employed as the dilatant polymer matrix, which is capable of combining the inherent material properties of different matrices, and which is more conducive to regulating the dilatancy and other overall properties of the material. The rubber matrix includes, as examples, but is not limited to, silicone rubber, ethylene propylene diene rubber, natural rubber, isoprene rubber, styrene butadiene rubber, neoprene rubber, nitrile rubber, and fluororubber.

Based on the structural characteristics of the dilatant hybrid dynamic polymer and the common covalent crosslinking action, dynamic covalent bond and non-covalent action contained in the dilatant hybrid dynamic polymer, the dilatant hybrid dynamic polymer has good dilatant property, structural stability, shape memory and dynamic reversibility, can be applied to energy absorbing materials, and can be applied to household articles (pillows, mattresses, sofas and the like), sports equipment, footwear, protective equipment, traffic (engine shock absorption, seats, damping sheets, tires and the like), medical instruments, national defense, aviation, aerospace, building materials, commodity packaging, industrial protection, sound absorption, noise reduction, vibration absorption buffering and the like, and ductile materials, shape memory materials and the like to medical, aviation, aerospace, military and the like.

According to the invention, through reasonably regulating and controlling the glass transition temperature of the dilatant polymer, the dilatant polymer material has stable vitrification dilatant in a single temperature (narrow temperature range), a plurality of temperatures or a wide temperature range, and can better adapt to the requirements of application scenes at different temperatures on the dilatant performance of the material.

In the invention, the dilatant hybrid dynamic polymer contains common covalent crosslinking at gel points, can provide continuous structural support and mechanical strength for dilatant materials, can reduce the residual deformation of dilatant materials, and effectively avoids permanent plastic deformation. The existence of the common covalent cross-linking can also ensure that even if dynamic covalent bonds and non-covalent actions contained in the polymer are subjected to dynamic reversible transformation, the polymer can not be disintegrated, and the use safety and reliability are high. Dynamic covalent and/or non-covalent interactions are introduced into the dilatant hybrid dynamic polymer to obtain dynamic covalent and/or non-covalent dynamic properties and dynamic stimulus responsiveness. Based on the dynamic reversibility of the contained dynamic crosslinking, the molecular level and microcosmic self-repairing performance can be provided for the polymer, and the polymer can also be used as a sacrificial bond for absorbing energy, improving toughness and improving damage resistance. In particular, a weak dynamic cross-linking above the gel point is introduced into the polymer, which can also provide a shape memory function to the polymer together with a common covalent cross-linking; the high dynamic cross-linking is introduced into the polymer, so that the dynamic and dynamic dilatancy is provided, and the microscopic self-repairing of the damage of the material can be accelerated, the tear resistance of the material is improved, and the like.

The dilatant hybrid dynamic polymer of the present invention can also be applied to other various suitable fields according to the properties exhibited by the polymer, and can be expanded and implemented according to actual needs by those skilled in the art.

The present invention, and methods of achieving dilatancy, and methods of absorbing energy using the dilatancy hybrid dynamic polymers as energy absorbing materials, are described in further detail below in conjunction with certain embodiments. The present invention will be described in further detail with reference to specific examples, which are not intended to limit the scope of the invention.

Example 1

Pyridine is used as a catalyst, dichloromethane is used as a solvent, and the compound (a) reacts with excessive 4-vinyl benzoyl chloride to prepare a dynamic cross-linking agent; 110 mol equivalent of 1- (2-methyl hexyl) -4-vinylbenzene, 2 mol equivalent of dynamic cross-linking agent and 0.6 mol equivalent of benzoyl peroxide are taken and placed in a reaction vessel, dissolved by a proper amount of toluene, and stirred and reacted for 24 hours at 70 ℃ under nitrogen atmosphere, thus obtaining the dynamic covalent cross-linked polystyrene derivative. Then 60 mol equivalent of 1- (2-methyl hexyl) -4-vinylbenzene, 50 mol equivalent of styrene, 6 mol equivalent of polyethylene glycol dimethacrylate (molecular weight is 1000) and 0.6 mol equivalent of benzoyl peroxide are taken and placed in a reaction vessel, the total mass of the reactants is 100wt%, 70wt% of dynamic covalent cross-linked polystyrene derivative and 300wt% of dimethylformamide are added, stirring and swelling are carried out for 1h, and then the mixture is reacted for 24h at 70 ℃ in nitrogen atmosphere, thus obtaining the dilatant polymer organogel. The tensile strength of the dilatant gel was 4.2MPa and the elongation at break was 355%. When the dilatant gel has structural damage, microscopic self-repair of the damage can be realized by heating or ultraviolet irradiation. The dilatant organogel has dilatant and slow rebound resilience in a very wide temperature range, can be used as an automobile protection pillow, a headrest and the like for anti-collision and shock absorption, and can provide good comfort and avoid secondary damage.

Example 2

60 mol equivalent of 1- (2-methoxyethoxy) -4-vinylbenzene, 10 mol equivalent of compound (a), 10 mol equivalent of compound (b), 4 mol equivalent of N- (2- (4-vinylphenoxy) ethyl) acrylamide and 1.2 mol equivalent of divinylbenzene are taken, placed in a reaction vessel, dissolved with a proper amount of toluene, added with 0.4 mol equivalent of azobisisobutyronitrile, and stirred and reacted for 24 hours at 70 ℃ under nitrogen atmosphere to prepare the dilatant polymer organogel. The tensile strength of the gel was 1.1MPa, and the elongation at break was 540%. The dilatant gel has a glass transition temperature of 52 ℃ and contains abundant strong dynamic non-covalent effects, multiple dilatant properties are obtained, and the dilatant gel is prepared into a sample with a thickness of 2cm, and the impact force of the sample penetrating through the gel at 25 ℃ is 19.9KN according to the method of EN 1621-2012. The dilatant gel also has good tear resistance, can be used for commodity packaging, and can resist earthquake and collision and prevent articles from being damaged.

Example 3

Dispersing polyisoprene-b-poly (2-ethyl methacrylate) diblock copolymer and organic phase-change filler (the molecular formula of which is shown as formula (a)) in a selective solvent, obtaining nano micelle coated with the organic phase-change filler through a self-assembly process, and initiating crosslinking of a poly (2-ethyl methacrylate) shell by ultraviolet irradiation to obtain the polymer microsphere filled with the organic phase-change filler. Taking 1 molar equivalent of mercapto-terminated eight-arm polyethylene glycol and 8 molar equivalents of 2- (allyloxy) anthracene, placing the eight-arm polyethylene glycol and the 8 molar equivalents of 2- (allyloxy) anthracene in a reaction vessel, keeping the total mass of the reactants to be 100wt%, dissolving the reactants with a proper amount of dichloromethane, adding 0.1wt% benzoin dimethyl ether, and carrying out ultraviolet irradiation reaction for 15min under nitrogen atmosphere at 365nm to obtain the anthracene-terminated polyethylene glycol. Taking 0.8 molar equivalent of anthryl end-capped polyethylene glycol, 0.75 molar equivalent of copolyether diamine, 1.5 molar equivalent of polyoxypropylene triamine, 3 molar equivalent of 2, 2-bis (4-carboxyphenyl) hexafluoropropane, placing the mixture into a reaction vessel, keeping the total mass of the reactants to be 100wt%, dissolving the mixture by using a proper amount of tetrahydrofuran, adding 12 molar equivalent of N-hydroxysuccinimide and 12 molar equivalent of dicyclohexylcarbodiimide, stirring at room temperature under nitrogen atmosphere for reaction for 36h, adding 3.2 molar equivalent of cucurbituril [8] urea, continuing to react for 6h, then adding 140wt% of polyethylene glycol oligomer, 70wt% of nano calcium carbonate (with the length-diameter ratio of 4 and the length of 1 micron), 70wt% of polymer microsphere filled with organic phase change filler, 15wt% of nano silver and 8wt% of silane coupling agent KH560, uniformly mixing, pouring the mixture into a mould, and drying at 50 ℃ for 12h to obtain the dilatant oligomer swelling gel. The dilatant gel has low glass transition temperature, and has strong dynamic dipole-dipole action and host-guest action, and dispersed nanometer calcium carbonate particles, so that the dilatant gel has dilatant property in a wide temperature range and excellent tensile toughness and tear resistance. The dilatant gel was prepared into a sample with a thickness of 1cm and tested according to the EN1621-2012 method, and the impact forces transmitted by the sample at 25 ℃, 0 ℃ and-20 ℃ were 12.6KN, 13.9KN and 16.3KN, respectively. The dilatant gel also has the characteristics of skin-friendly, bacteriostasis and the like, can be used as a buffer insole of high-grade sports shoes for shock absorption and buffering, and the filled organic phase change filler can improve the comfort.

Example 4

And (2) taking 0.2 molar equivalent of mercapto-terminated eight-arm polyethylene glycol, 3.2 molar equivalent of mercapto-terminated ethylene oxide-propylene oxide copolymer and 4 molar equivalent of compound (a), placing the materials into a reaction vessel, recording the total mass of the reactants as 100wt%, dissolving the materials with a proper amount of dichloromethane, adding 0.1wt% benzoin dimethyl ether, and carrying out ultraviolet irradiation reaction for 15min under nitrogen atmosphere at 365nm to obtain the dynamic siloxane bond crosslinked polyethylene glycol. Taking 1 molar equivalent of mercapto-terminated eight-arm polyethylene glycol and 4 molar equivalents of methylene bisacrylamide, placing the eight-arm polyethylene glycol and the 4 molar equivalents of methylene bisacrylamide into a reaction container, keeping the total mass of the reactants to be 100wt%, dissolving the reactants with a proper amount of methylene dichloride, adding 75% of dynamic siloxane bond crosslinked polyethylene glycol and 0.1% of benzoin dimethyl ether, stirring and swelling for 30min, and then carrying out ultraviolet irradiation reaction for 15min under nitrogen atmosphere at 365nm to obtain the double-network polyethylene glycol. 80g of double-network polyethylene glycol, 1.6g of tetramethyl ammonium hydroxide and 0.6g of sodium dodecyl benzene sulfonate are taken and swelled in 1-hydroxyethyl-3-methylimidazole tetrafluoroborate ionic liquid, so as to obtain the dilatant ionic liquid swelling gel. The dilatant gel had a tensile strength of 7.4MPa, an elongation at break of 685%, a toughness of 25.8MPa and a tear strength of 8.2KN/m, and was prepared into a sample having a thickness of 1cm, and the impact forces transmitted by the sample at 25℃and 60℃were respectively 12.8KN and 18.4KN, as measured by the method of EN 1621-2012. The dilatant gel in the embodiment also has better heat conductivity, can be used as a buffer material, and can be applied to fitness equipment or medical equipment for buffer and anti-collision.

Example 5

Putting 1 molar equivalent of the compound (a) and 3.3 molar equivalents of the compound (b) into a reaction vessel, dissolving with a proper amount of dimethylformamide, adding 0.15 molar equivalent of the photoinitiator 184, and carrying out ultraviolet irradiation reaction for 2.5 hours at 365nm under nitrogen atmosphere to obtain terpyridyl modified polyether; then 0.25 molar equivalent of compound (a), 0.75 molar equivalent of end mercapto ethylene oxide-propylene oxide copolymer, 0.8 molar equivalent of terpyridyl modified polyether and 1.5 molar equivalent of compound (c) are taken and placed in a reaction vessel, dissolved by a proper amount of tetrahydrofuran, then 0.15 molar equivalent of 4-dimethylaminopyridine is added, and stirring reaction is carried out for 8 hours at 65 ℃ to prepare the dilatant elastomer, then one surface of the elastomer is coated with 0.02mol/L of methanol solution of ferric (II) sulfate heptahydrate, the coating times are 5 times, and after each coating, the coating is dried at 60 ℃ for 10 minutes, and then the next coating is carried out, thus finally obtaining the dilatant elastomer with a gradient crosslinking structure. The dilatant elastomer has room temperature dilatant, slow rebound resilience and shape memory, has a tensile strength of 32.8MPa, an elongation at break of 560%, a material toughness of 94.8MPa and a tear strength of 33.6KN/m, and is prepared into a sample with a thickness of 1cm, and the sample is tested according to the method EN1621-2012, and the transmitted impact force is 11.2KN at room temperature. Because the dilatant elastomer has the characteristic of gradient crosslinking, the two sides of the dilatant elastomer have different strength and hardness, and when the dilatant elastomer is used as an energy absorbing material (such as a sports protective tool), the softer side can be attached to a human body, so that the comfort is improved; the surface with higher strength can be more effectively impact-resistant, and the practicability and the comfort are very strong.

Example 6

Taking 0.75 molar equivalent polytetrahydrofuran glycol (molecular weight is 250 Da), 0.25 molar equivalent polytetrahydrofuran glycol (molecular weight is 650 Da), 0.25 molar equivalent polytetrahydrofuran glycol (molecular weight is 2000 Da), 0.75 molar equivalent polytetrahydrofuran glycol (molecular weight is 5000 Da) and 1.7 molar equivalent compound (a), placing the materials into a reaction vessel, dissolving the materials with proper amount of chloroform, adding 2 molar equivalent 4-dimethylaminopyridine and 8 molar equivalent dicyclohexylcarbodiimide, stirring the materials at room temperature for reaction for 24 hours, adding a chloroform solution with 0.2 molar equivalent trimesic acid, continuing stirring the materials for reaction for 16 hours, and removing impurities and solvents after the reaction is finished to obtain a purified product; and swelling the purified product in chloroform, dropwise adding an acetonitrile solution of 0.02mol/L zinc trifluoromethane sulfonate under stirring, continuing stirring for reaction for 1h after the dropwise adding is finished, and then drying to obtain the dilatant polymer elastomer. The dilatant elastomer had a stable dilatant property over a wide temperature range and was prepared as a test specimen having a thickness of 2cm and tested according to EN1621-2012 to give a transmitted impact force of 18.8KN at 25 ℃. When the elastomer is subjected to local damage, the local damage repair can be realized based on the dynamic reversibility of the tridentate metal-ligand effect, and the elastomer can be used as a damping material for damping.

Example 7

Nano calcium carbonate (length-diameter ratio is 4 and length is about 1 micron) is dispersed in polyethylene glycol (molecular weight is 200 Da) to obtain a dilatant dispersion liquid with volume fraction of 45%, and the dilatant dispersion liquid is filled into polyacrylate hollow spheres to obtain the polyacrylate microspheres filled with the dilatant dispersion liquid, wherein the filling rate is about 60%. In a torque rheometer, ethylene propylene diene monomer is used as a matrix, benzoyl peroxide is used as an initiator, maleic anhydride is used as a monomer, and a melt grafting technology is adopted to prepare the maleic anhydride grafted ethylene propylene diene monomer, wherein the mass ratio of the ethylene propylene diene monomer to the benzoyl peroxide to the maleic anhydride is 100:1:20, the reaction temperature is 170 ℃, the reaction time is 30min, and the rotor rotating speed is 50r/min. 40g of maleic anhydride grafted ethylene propylene diene monomer and 15g of polyacrylate microsphere filled with dilatant dispersion are placed in a reaction vessel, 80mL of xylene solvent is added, the mixture is heated to 45 ℃ and stirred for 30min, then 0.88g of compound (a), 0.6g of hexanediol, 0.7g of p-toluenesulfonic acid, 0.3g of polyethylene wax, 0.15g of dibutyl tin maleate, 0.8g of aluminum nitride, 0.2g of silane coupling agent KH560 and 0.12g of antioxidant BHT are added, and then the mixture is stirred and reacted for 6h at 80 ℃ in nitrogen atmosphere, and after the reaction is finished, the mixture is dried, thus obtaining the dilatant elastomer with slow rebound resilience. The dilatant elastomer has low glass transition temperature, contains strong dynamic saturated five-membered ring organic borate bond and dilatant dispersion liquid, and still has dilatant at-40 ℃; due to the existence of a common covalent cross-linking structure, the elastomer can keep stable shape when the temperature is increased; when the structure is damaged, the damage repair can be realized through the reversible process of the dynamic crosslinking effect, and the device can be used as an automobile vibration damping accessory, such as an engine vibration damping sheet for vibration damping, and can adapt to vibration damping requirements at different temperatures.

Example 8

Nano calcium carbonate (length-diameter ratio is 4 and length is about 1 micron) is dispersed in polyethylene glycol (molecular weight is 200 Da) to obtain a dilatant dispersion liquid with volume fraction of 45%, and the dilatant dispersion liquid is filled into polyacrylate hollow spheres to obtain the polyacrylate microspheres filled with the dilatant dispersion liquid, wherein the filling rate is about 60%. 45 parts by mass of bisphenol A diglycidyl ether, 55 parts by mass of epoxy silicone oil (the chemical formula is shown as a formula (a), the molecular weight of the epoxy silicone oil is 2000 Da) and 40 parts by mass of polyacrylate microspheres filled with dilatant dispersion liquid are taken, and placed in a container, and heated to 75 ℃ to obtain a slow rebound component A; 6 parts by mass of foaming agent Celogen-OT, 3 parts by mass of surfactant Pluronic L-64, 1.5 parts by mass of sodium lauryl sulfate, 0.5 part by mass of pore-forming agent, 1.5 parts by mass of antistatic agent SN and 8 parts by mass of toluene are taken, placed in another container, and stirred and mixed uniformly to obtain a slow rebound component B; then adding the component B into the component A, stirring and mixing uniformly at a high speed, adding 10 parts by mass of the compound (B) and 50 parts by mass of p-aminodiphenyl ether (slow rebound component C), placing the materials into a mold coated with a release agent, heating to 120 ℃ for foaming, and curing the obtained foam body at 80 ℃ for 2 hours to prepare the dilatant polymer foam with slow rebound resilience. The dilatant foam has the characteristics of excellent molding stability, moisture resistance, solvent resistance, heat insulation, flame retardance and the like. The dilatant foam has dilatant and slow rebound resilience in a wide temperature range, and can be used as a protective helmet, an explosion-proof helmet and the like to resist impact.

Example 9

Toluene is taken as a solvent, and the compound (a) reacts with 10 times of hexamethylene diisocyanate to prepare modified isocyanate; taking 75 parts by mass of polyether polyol (hydroxyl value of 54-58 mgKOH/g), 25 parts by mass of palm oil polyol (hydroxyl value of 215-245mgKOH/g, functionality of 3), 20 parts by mass of hexamethylene diisocyanate and 0.4 part by mass of stannous octoate, placing the materials into a reaction container, heating to 80 ℃ for reaction for 6 hours, then adding 20 parts by mass of modified isocyanate and 8.8 parts by mass of zinc triflate, mixing uniformly, and placing the materials into a mold for continuous reaction for 2 hours to obtain a polyurethane elastomer; and then placing the elastomer with half thickness into an acrylic ester reaction solution, wherein the acrylic ester reaction solution contains monomer phenyl acrylate, a crosslinking agent is a compound (b), and a photoinitiator 2-hydroxyethyl-2-methyl propiophenone, the molar ratio of the three is 6:1:0.08, taking out the elastomer after impregnation is finished, and irradiating one side of the impregnation reaction solution by 365nm ultraviolet light to initiate polymerization to obtain the dilatant elastomer with a gradient crosslinking structure. The two sides of the dilatant elastomer have different crosslinking forms and crosslinking degrees, so that the two sides of the dilatant elastomer have different strength and hardness, and when the dilatant elastomer is used as an energy absorbing material (such as a sports protective tool), the softer side can be attached to a human body, and the comfort is improved; the surface with higher strength can be more effectively impact-resistant, and the practicability and the comfort are very strong.

Example 10

1 mol equivalent of ethyl hydrogen silicone oil, 8 mol equivalent of compound (a) and 2mol equivalent of dimethyl divinyl silane are taken and placed in a reaction vessel, a proper amount of toluene is used for dissolution, a small amount of xylene solution of platinum (0) -1, 3-diethylene-1, 3-tetramethyl disiloxane complex (the platinum content is 0.003 wt%) is added, stirring reaction is carried out for 48 hours at 60 ℃ under argon atmosphere, and impurities and solvents are removed after the reaction is finished, so as to obtain a purified product; and swelling the purified product in chloroform, dropwise adding an acetonitrile solution of 0.02mol/L zinc trifluoromethane sulfonate under stirring, continuing stirring for reaction for 1h after the dropwise adding is finished, and then drying to obtain the dilatant polymer elastomer. The dilatant elastomer has a glass transition temperature of-40 ℃ and contains a toothed metal-ligand effect, so that the dilatant elastomer has excellent low-temperature dilatant property and material toughness, the tensile strength is 9.7MPa, the elongation at break is 1135%, the material toughness is 58.8MPa, the tearing strength is 10.2KN/m, a sample with a thickness of 1cm is prepared, and the impact forces transmitted by the sample at 25 ℃ and-40 ℃ are 16.1KN and 17.5KN respectively according to the method of EN 1621-2012. The dilatant elastomer also has good corrosion resistance, and can be used as a sealing element in a deep sea detector and a ship for shock absorption and sealing.

Example 11

2-amino ethyl acrylate is used as a polymerization monomer, azodiisobutyronitrile is used as a free radical initiator, dimethyl sulfoxide is used as a solvent, and a homopolymer with amino-containing side groups is prepared through free radical polymerization; and then taking methylene dichloride as a solvent, and carrying out graft modification on the homopolymer by using acryloyl chloride, wherein the molar ratio of amino to acryloyl chloride is 3:1, so as to prepare the homopolymer with the side group containing amino and acrylate groups. Triethylamine is used as a catalyst, methylene dichloride is used as a solvent, hydroxyl-terminated ethylene oxide-propylene oxide copolymer and succinic anhydride react for 4 hours at room temperature under stirring in nitrogen atmosphere, and then reflux reaction is carried out for 1 hour, so that the carboxyl double-terminated ethylene oxide-propylene oxide copolymer is prepared; taking 3 molar equivalents of carboxyl double-end capped ethylene oxide-propylene oxide copolymer, 1 molar equivalent of compound (a) and 2 molar equivalents of pentaerythritol, placing the copolymer in a reaction vessel, keeping the total mass of the reactants to be 100wt%, dissolving the copolymer in an appropriate amount of tetrahydrofuran, adding 4 molar equivalents of 4-dimethylaminopyridine and 16 molar equivalents of dicyclohexylcarbodiimide, stirring the mixture at room temperature for reaction for 24 hours, and removing impurities and solvents after the reaction is finished to obtain a purified product. 15g of homopolymer with side groups containing amino groups and acrylate groups, 85g of purified product and 20g of submicron silicon dioxide are taken and swelled in 1-hydroxyethyl-3-methylimidazole tetrafluoroborate ionic liquid, so as to obtain the dilatant ionic liquid swelling gel. The dilatant gel has a glass transition temperature of 43 ℃ and has dispersed therein non-crosslinked dilatant polymer and submicron silica to obtain vitrified dilatant, dynamic dilatant and dispersive dilatant. The dilatant gel had a tensile strength of 3.1MPa, an elongation at break of 725% and a toughness of 12.5MPa, and was prepared into a sample having a thickness of 1cm, and the impact forces of the sample transmitted at 25℃and 45℃were 12.5KN and 12.8KN, respectively, as measured by the method of EN 1621-2012. When the dilatant gel is damaged such as cracks, the dilatant gel can be heated to 120 ℃ or irradiated by ultraviolet light to realize reversible fracture of a dynamic covalent bond, generate free radicals and initiate free radical polymerization of acrylate side groups, so that a novel covalent cross-linked network is obtained, and the aims of repairing the damage, recovering the mechanical strength and improving the damage resistance are fulfilled. The dilatant gel in the embodiment can be used for manufacturing bulletproof clothes or explosion-proof clothes, wherein common covalent crosslinking can provide good structural support, has the flexibility of the gel, and is convenient for wearing and acting; and simultaneously, the bullet and puncture resistance can be realized, and the damage repair can be realized after the damage occurs.

Example 12

Taking 0.5 molar equivalent of the compound (a) and 0.75 molar equivalent of 1, 6-hexanediol, placing the compound (a) and the 0.75 molar equivalent of the 1, 6-hexanediol into a reaction vessel, adding 0.02wt% of tetra-n-butyl titanate catalyst, stirring and reacting for 4 hours at 170 ℃ under nitrogen atmosphere, heating to 220 ℃, controlling the pressure to be 0.4KPa, and continuing to react for 10 hours to obtain the hydroxyl-terminated liquid crystal prepolymer. And (3) taking 1 molar equivalent of carboxyl-terminated four-arm polyethylene glycol, 1 molar equivalent of hydroxyl-terminated polypropylene oxide and 1 molar equivalent of compound (b), placing the materials into a reaction vessel, dissolving the materials with proper amount of tetrahydrofuran, then adding 2 molar equivalents of 4-dimethylaminopyridine and 8 molar equivalents of dicyclohexylcarbodiimide, and stirring the materials at room temperature for reaction for 24 hours to obtain the inorganic boron anhydride bond crosslinked dynamic polymer. And then taking 1 mole equivalent of carboxyl end-capped four-arm polyethylene glycol and 2 mole equivalent of hydroxyl end-capped liquid crystal prepolymer, placing the prepolymer into a reaction vessel, keeping the total mass of the reactants as 100wt%, dissolving the prepolymer with proper amount of tetrahydrofuran, adding 80wt% of inorganic boric anhydride bond-crosslinked dynamic polymer, stirring and swelling for 30min, adding 2 mole equivalent of 4-dimethylaminopyridine and 8 mole equivalent of dicyclohexylcarbodiimide, stirring and reacting for 24h at room temperature, and removing the solvent after finishing the reaction to obtain the dilatant polymer elastomer. The dilatant elastomer has good low temperature resistance and can absorb energy in a wider temperature range. The dilatant elastomer has tensile strength of 7.9MPa, elongation at break of 545%, toughness of 25.2MPa and tearing strength of 16.2KN/m, and can be used as a vibration reduction sealing material for buffering and vibration reduction and has the functions of isolating and sealing.

Example 13

And (2) taking 0.4 molar equivalent of polyethylene glycol, 0.8 molar equivalent of hydroxyl-terminated ethylene oxide-propylene oxide copolymer and 1 molar equivalent of compound (a), placing the materials into a reaction vessel, dissolving the materials with proper amount of tetrahydrofuran, then adding 1 molar equivalent of 4-dimethylaminopyridine and 4 molar equivalent of dicyclohexylcarbodiimide, stirring the materials at room temperature for reaction for 24 hours, adding 0.5 molar equivalent of n-butyric acid, continuing the reaction for 12 hours, and removing impurities and solvent after the reaction is finished to obtain the non-crosslinked dilatant polymer. 100 mol equivalent of methacrylic acid (2-methoxyethyl) ester, 40 mol equivalent of compound (b), 20 mol equivalent of 2-naphthyl acrylate, 3.5 mol equivalent of methylene diacrylate and 0.25 mol equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, the total mass of the reactants is 100wt percent, the reactants are dissolved by using a proper amount of tetrahydrofuran, 100wt percent of non-crosslinked dilatant polymer is added, and after stirring and dissolution, the mixture is reacted for 24 hours at 70 ℃ under nitrogen atmosphere, and then dried to obtain the dilatant polymer elastomer. The dilatant elastomer has rich non-covalent crosslinking effect, and provides good mechanical strength, material toughness and tear resistance together with common covalent crosslinking. When scratches appear on the surface of the dilatant elastomer, the scratches can be repaired by local heating. The dilatant elastomer has stable dilatant and slow rebound from 0 ℃ to 30 ℃, can be used as a self-repairable automobile interior material for sound insulation and noise reduction, and can improve comfort and avoid secondary injury due to slow rebound.

Example 14

120 molar equivalents of ethyl acrylate, 20 molar equivalents of hydroxyethyl acrylate, 0.12 molar equivalents of compound (a) and 1 molar equivalent of pentamethyldiethylenetriamine are taken and placed in a reaction vessel, dissolved by a proper amount of tetrahydrofuran, bubbling nitrogen to remove oxygen for 30min, then 1 molar equivalent of cuprous bromide is added, and stirring reaction is carried out for 48h at 80 ℃ under argon atmosphere, thus obtaining the bromine-terminated multi-arm acrylate homopolymer. Taking 1 molar equivalent of a bromine-terminated multi-arm acrylate homopolymer and 4 molar equivalents of a compound (b), placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of dimethylformamide, adding 12 molar equivalents of pyridine catalyst, and stirring the mixture under nitrogen atmosphere for reaction for 12 hours to prepare a hydrogen bond group modified homopolymer I; then taking 1 mol equivalent of bromine-terminated multi-arm acrylate homopolymer and 4 mol equivalent of compound (c), placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of dimethylformamide, adding 12 mol equivalent of pyridine catalyst, and stirring the mixture under nitrogen atmosphere for reaction for 12 hours to prepare hydrogen bond group modified homopolymer II; then 1 mole equivalent of bromine-terminated multi-arm acrylate homopolymer, 0.5 mole equivalent of hydrogen bond group modified homopolymer I, 0.5 mole equivalent of hydrogen bond group modified homopolymer II and 1 mole equivalent of pentaerythritol tetra (3-mercaptopropionic acid) are taken and placed in a reaction vessel, dissolved by a proper amount of dimethylformamide, then 12 mole equivalents of pyridine catalyst are added, and then stirring reaction is carried out for 12 hours under nitrogen atmosphere, and then the dilatant polymer elastomer is obtained after drying. When the temperature is reduced to-20 ℃, the dilatant elastomer remains dilatant without significant hardening and embrittlement problems. The dilatant elastomer also has a shape memory function, can be used as a shape memory material, and is applied to medical instruments for buffering to prevent personnel and articles from being damaged.

Example 15

The dynamic polymer is prepared by free radical polymerization reaction by taking azodiisobutyronitrile as an initiator, taking a compound (a) as a polymerization monomer and tetrahydrofuran as a solvent. 180 molar equivalents of 2- (2-phenoxyethoxy) ethyl acrylate, 0.48 molar equivalent of compound (b) and 1 molar equivalent of pentamethyl diethylenetriamine are taken and placed in a reaction vessel, dissolved by using a proper amount of tetrahydrofuran, bubbling nitrogen to remove oxygen for 30min, then adding 1 molar equivalent of cuprous bromide, stirring and reacting for 48h at 80 ℃ under argon atmosphere, and purifying to obtain a bromine-terminated multi-arm acrylate homopolymer after finishing the reaction; taking 4 molar equivalents of bromine-terminated multi-arm acrylate homopolymer, 2 molar equivalents of compound (c) and 2 molar equivalents of pentaerythritol tetra (3-mercaptopropionic acid), placing the mixture into a reaction vessel, keeping the total mass of the reactants as 100wt%, dissolving the mixture with a proper amount of dimethylformamide, adding 60wt% of dynamic polymer and 36 molar equivalents of pyridine catalyst, stirring the mixture under nitrogen atmosphere for reaction for 12 hours, and removing impurities and solvents after the reaction is finished to obtain a purified product; 45g of the purified product, 1.5g of zinc acetate, 40g of PMMA (particle size of 2.5 μm) and 0.12g of sodium dodecyl benzene sulfonate were taken and swollen in glycerol to obtain a dilatant polymer organogel. The dilatant gel has a glass transition temperature of 10 ℃ and contains strong dynamic hydrogen bonding action and solid microparticles dispersed therein, so that the dilatant gel does not harden and embrittle at 0 ℃ and is prepared into a sample with a thickness of 1cm, and according to the method of EN1621-2012, the impact force transmitted by the sample at 25 ℃ and 0 ℃ is 13.5KN and 14.1KN respectively, and the dilatant gel can be used as a damping material and applied to the field of automobile industry for damping and shock absorption.

Example 16

Taking 100 molar equivalents of benzyl acrylate, 40 molar equivalents of vinyl isopropyl ether, 60 molar equivalents of compound (a), 4 molar equivalents of methylene diacrylate and 0.8 molar equivalent of azobisisobutyronitrile, placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of tetrahydrofuran, and stirring the mixture at 70 ℃ for reaction for 24 hours under nitrogen atmosphere to prepare a single network copolymer; taking 100 mol equivalent of benzyl acrylate, 12 mol equivalent of 2-isocyanoethyl acrylate and 0.8 mol equivalent of azodiisobutyronitrile, placing the mixture into a reaction vessel, keeping the total mass of the reactants as 100wt%, adding a proper amount of tetrahydrofuran solvent, adding 40wt% of single-network polyacrylate, stirring and swelling for 30min, stirring and reacting at 70 ℃ for 24h under nitrogen atmosphere, adding 6 mol equivalent of dimethylglyoxime, and continuing to react for 12h to obtain the double-network copolymer. 50g of double-network copolymer and 15g of nano silicon dioxide are taken and swelled in 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid, and a dilatant ionic liquid swelling gel is obtained. The dilatant gel has room temperature dilatancy and room temperature slow rebound resilience, the tensile strength is 13.7MPa, the elongation at break is 450%, the toughness of the material is 34.5MPa, the tearing strength is 25.2KN/m, the dilatant gel is prepared into a sample with the thickness of 1cm, and the transmitted impact force at 25 ℃ is 18.9KN according to the method of EN 1621-2012. The dilatant gel also has self-adhesive property and puncture resistance, and can be adhered to corners, sharp objects and the like for buffering, so that personnel injury is reduced.

Example 17

Taking 40 molar equivalents of the mesogen compound (a), 1 molar equivalent of tetramethylpiperidine oxynitride and 0.4 molar equivalent of benzoyl peroxide, placing the mesogen compound (a), 1 molar equivalent of tetramethylpiperidine oxynitride and 0.4 molar equivalent of benzoyl peroxide into a reaction vessel, dissolving the mesogen compound with proper amount of dimethylbenzene, then reacting for 3 hours at 90 ℃ under nitrogen atmosphere, and then heating to 120 ℃ to react for 15 hours to prepare a liquid crystal homopolymer; and then taking the liquid crystal homopolymer as a macromolecular chain transfer agent, taking paraxylene as a solvent, taking n-octyl acrylate as a soft segment monomer, wherein the molar ratio of the chain transfer agent to the soft segment monomer is 1:160, and reacting for 18 hours at 120 ℃ in nitrogen atmosphere to obtain the segmented copolymer. 60 molar equivalents of n-octyl acrylate, 12 molar equivalents of 2- (isopropylamino) ethyl acrylate and 0.4 molar equivalent of benzoyl peroxide are taken and placed in a reaction vessel, dissolved by using an appropriate amount of tetrahydrofuran, and then reacted for 16 hours at 70 ℃ under a nitrogen atmosphere to prepare the acrylate copolymer. 120 mol equivalent of n-octyl acrylate, 5 mol equivalent of compound (b), 1 mol equivalent of methylene bisacrylamide and 0.8 mol equivalent of benzoyl peroxide are taken and placed in a reaction vessel, the total mass of the reactants is 100wt percent, the reactants are dissolved by proper amount of toluene, 60wt percent of block copolymer and 40wt percent of acrylic ester copolymer are added, stirred and mixed for 30min, and the mixture is reacted for 24h at 70 ℃ under nitrogen atmosphere and then dried to obtain the dilatant polymer elastomer. The dilatant elastomer has dilatant property in a wider temperature range, has a tensile strength of 16.6MPa, an elongation at break of 323 percent, a material toughness of 27.5MPa and a tearing strength of 23.8KN/m, is prepared into a sample with a thickness of 1cm, and can be used as a toughness material, such as a sealing rubber strip for shock absorption and sealing isolation according to the method of EN1621-2012, wherein the impact force transmitted by the sample at 40 ℃, 25 ℃ and-20 ℃ is 8.6KN, 7.3KN and 12.8KN respectively.

Example 18

Preparing a dynamic cross-linking agent by reacting a compound (a) with excessive acryloyl chloride by using triethylamine as a catalyst and methylene dichloride as a solvent; 120 molar equivalents of 2- (2-phenoxyethoxy) ethyl acrylate, 30 molar equivalents of vinyl butyl ether, 2 molar equivalents of diethylene glycol diacrylate, 2 molar equivalents of the dynamic cross-linking agent prepared by the method and 0.8 molar equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, dissolved by using a proper amount of tetrahydrofuran, and then reacted for 36 hours at 70 ℃ under nitrogen atmosphere to prepare a copolymer; 60g of copolymer, 35g of PMMA particles (particle size of 2.5 μm), 20g of polyvinyl alcohol and 5g of graphene are taken and swelled in glycerol to obtain a dilatant polymer organogel. The dilatant gel has multiple dilatant and slow rebound resilience, and can be used as sports protection devices, such as knee pads, elbow pads and the like, for shock resistance.

Example 19

Taking 80 molar equivalents of vinyl propyl ether, 40 molar equivalents of ethyl 2- (phenylthio) acrylate and 0.8 molar equivalent of azodiisobutyronitrile, placing the materials into a reaction vessel, dissolving the materials with a proper amount of dimethylformamide, and then reacting the materials for 36 hours at 70 ℃ under a nitrogen atmosphere to obtain a copolymer; then 60 mol equivalent of isobornyl methacrylate, 0.5 mol equivalent of methylene diacrylate, 0.5 mol equivalent of compound (a), 15 mol equivalent of compound (b) and 0.65 mol equivalent of azobisisobutyronitrile are taken and placed in a reaction vessel, the total mass of the reactants is 100wt%, 60wt% of copolymer is added, a proper amount of dimethylformamide is used for dissolution, and then the mixed solution is placed in a mould for reaction at 70 ℃ for 36 hours, thus obtaining the dilatant polymer organogel. The tensile strength of the dilatant gel is 3.8MPa, the elongation at break is 560%, the dilatant gel is prepared into a sample with the thickness of 1cm, and according to the method EN1621-2012, the impact forces of the sample penetrating at 25 ℃ and minus 30 ℃ are 18.2KN and 19.8KN respectively, so that the dilatant gel can be used as a shock absorbing shoe material and can play a good role in buffering and shock absorption even in winter.

Example 20

80 molar equivalents of ethyl methacrylate, 20 molar equivalents of beta-hydroxypropyl methacrylate and 0.8 molar equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, dissolved by a proper amount of tetrahydrofuran, and then stirred and reacted for 24 hours at 70 ℃ under nitrogen atmosphere, so as to prepare the acrylate copolymer with the pendant group containing a hydrogen bond group. Using triethylamine as a catalyst and methylene dichloride as a solvent, and reacting a compound (a) and a compound (b) with excessive acryloyl chloride to prepare acrylic ester I and acrylic ester II; 70 mol equivalent of ethyl methacrylate, 15 mol equivalent of acrylic ester I, 15 mol equivalent of acrylic ester II and 0.8 mol equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, dissolved by a proper amount of tetrahydrofuran, and then stirred and reacted for 24 hours at 70 ℃ under nitrogen atmosphere, so that the supermolecule crosslinked acrylic ester copolymer is prepared. 80 molar equivalent of ethyl methacrylate, 5 molar equivalent of methylene bisacrylamide and 0.8 molar equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, a proper amount of tetrahydrofuran solvent is added, 40 weight percent of acrylate copolymer containing a monodentate hydrogen bond group and 80 weight percent of supermolecule crosslinked acrylate copolymer are added, stirred and mixed for 30min, and reacted for 24h at 70 ℃ under nitrogen atmosphere, and then dried to obtain the dilatant polymer elastomer. The dilatant elastomer has two glass transition processes, namely at-23 ℃ to 15 ℃ and 20 ℃ to 69 ℃, contains abundant strong dynamic supermolecule effect, and has dilatant, slow rebound and energy absorption in a wide temperature range. The tensile strength of the dilatant elastomer is 18.7MPa, the elongation at break is 652%, the toughness of the material is 60.3MPa, the tearing strength is 44.2KN/m, and when structural damage occurs in the dilatant elastomer, the dilatant elastomer can also realize self-repairing and can be used as a sports protective tool to carry out impact protection.

Example 21

Taking 100 molar equivalents of 2- (2-phenoxyethoxy) ethyl acrylate, 20 molar equivalents of polyethylene glycol monomethacrylate, 1 molar equivalent of polyethylene glycol dimethacrylate and 0.2 molar equivalent of azodiisobutyronitrile, placing the materials into a reaction vessel, dissolving the materials with proper tetrahydrofuran, stirring the materials at 70 ℃ under nitrogen atmosphere for reaction for 24 hours, and removing impurities and solvent after finishing the reaction to obtain the single network polyacrylate. Taking 100 molar equivalents of 2- (2-phenoxyethoxy) ethyl acrylate, 4 molar equivalents of compound (a), 4 molar equivalents of compound (b) and 0.2 molar equivalent of azobisisobutyronitrile, placing the materials into a reaction vessel, recording the total mass of the reactants as 100wt%, adding 80wt% of single network polyacrylate, fully swelling the materials with proper tetrahydrofuran, stirring the materials at 70 ℃ for reaction for 24 hours under nitrogen atmosphere, and purifying the materials after finishing the reaction to obtain the double network polymer. 120 mol equivalent of 2- (2-phenoxyethoxy) ethyl acrylate, 12 mol equivalent of 2- (methacryloyloxy) ethyl trimethyl ammonium chloride and 0.2 mol equivalent of azodiisobutyronitrile are taken and placed in a reaction vessel, the total mass of the reactants is 100wt%, 90wt% of a double-network polymer is added, a proper amount of tetrahydrofuran is used for fully swelling, stirring reaction is carried out for 24 hours at 70 ℃ in a nitrogen atmosphere, and purification is carried out after the reaction is finished, so as to obtain a purified product; 10g of bismuth oxychloride (6 microns) was dispersed in 100mL of 0.02mol/L sodium polyacrylate aqueous solution, 45g of the purified product was then added, and the mixture was stirred, swollen and mixed at 45℃for 6 hours to obtain a dilatant polymer hydrogel. The multiple crosslinked networks of the dilatant gel act synergistically to provide the gel with excellent mechanical strength, material toughness, tear resistance and energy absorption, and the tensile strength is 25.1MPa, the elongation at break is 480%, the material toughness is 63.5MPa, and the tear strength is 33.4KN/m. The dilatant gel has a large glass transition temperature span, contains abundant strong dynamic cross-links and is dispersed with bismuth oxychloride microparticles, has dilatancy in a wide temperature range, and is prepared into a sample with a thickness of 1cm, and the impact forces of the sample penetrating at 60 ℃, 25 ℃ and minus 20 ℃ are respectively 14.2KN, 10.1KN and 10.9KN according to the method of EN1621-2012, so that the sample can be used as an anti-explosion material to resist impact and explosion.

Example 22

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Uniformly mixing 50 parts by mass of a copolymer of hydroxyl-terminated ethylene oxide and propylene oxide, 20 parts by mass of hydroxyl-terminated ethylene oxide, 15 parts by mass of hydroxyl-terminated butylbenzene liquid rubber, 15 parts by mass of a compound (a), 8 parts by mass of tri (2-hydroxyethyl) amine, 3 parts by mass of multi-walled carbon nanotubes, 12 parts by mass of tricresyl phosphate and 0.6 part by mass of stannous octoate to obtain a slow rebound material A; taking 56 parts by mass of diphenylmethane diisocyanate (slow rebound material B), adding the diphenylmethane diisocyanate into the slow rebound material A, uniformly stirring, placing the mixture in a mould, reacting at 45 ℃ for 12 hours, then reacting at 75 ℃ for 6 hours, and finally heating to 90 ℃ for 30 minutes to obtain the dilatant polymer elastomer with slow rebound. The elastomer has stable dilatancy and slow rebound resilience in a wider temperature range, is prepared into a sample with the thickness of 1cm, and has the impact forces of 12.7KN and 14.4KN respectively when the sample is measured at 25 ℃ and 40 ℃ below zero according to the EN1621-2012 method, the dilatancy elastomer is repeatedly extruded and bent, cannot generate permanent deformation, can be used as an automotive interior material, is buffered and provides good comfort, and can also maintain good touch texture when the temperature is reduced.

Example 23

Under the catalysis of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, hydroxypropyl end-capped polydimethylsiloxane with the molar ratio of 1:1.05 reacts with the compound (a) to prepare polysiloxane containing inorganic boric acid monoester bonds. 60 parts by mass of castor oil polyether polyol (with the hydroxyl value of 160 mgKOH/g), 35 parts by mass of polyacrylate polyol P90 (with the hydroxyl value of 90mgKOH/g and the functionality of 6), 5 parts by mass of polyester diol-2047A (with the hydroxyl value of 280 mgKOH/g), 2 parts by mass of pore-forming agent K-0601, 2.5 parts by mass of water, 1.5 parts by mass of organosilicon foam stabilizer, 0.6 part by mass of stannous octoate, 0.4 part by mass of amine catalyst LV-33, 50 parts by mass of polysiloxane containing inorganic boric acid monoester bond and 5.5 parts by mass of polyethylene glycol-polysiloxane copolymer are added into a reaction vessel, and uniformly stirred to obtain a material A, wherein the material temperature is controlled to be 23 ℃; taking 55 parts by mass of toluene diisocyanate to obtain a material B, and controlling the material temperature to be 23 ℃; and adding the material B into the material A, stirring and mixing for 6s at 3000rpm, and then placing the mixture into a die at 120 ℃ for curing for 25min to obtain the dilatant polymer foam. The foam was prepared into a sample having a thickness of 1cm, and the impact forces of foam permeation were measured at 60 ℃, 25 ℃ and-60 ℃ according to EN1621-2012 to be 11.8KN, 8.2KN and 9.2KN, respectively. The data show that the polymer foam with multiple dilatancy can maintain very stable energy absorption at low temperature, room temperature and medium temperature, can be used as an engine damping material for damping, and can play an effective damping role in both cold winter and hot summer.

Example 24

In a torque rheometer, ethylene propylene diene monomer is used as a matrix, benzoyl peroxide is used as an initiator, a compound (a) and cashew nut shell oil are used as grafting monomers, and a double-monomer melt grafting method is adopted to prepare the grafted modified ethylene propylene diene monomer, wherein the mass ratio of the ethylene propylene diene monomer to the benzoyl peroxide to the compound (a) to the cashew nut shell oil is 100:0.8:20:10, the reaction temperature is 135 ℃, the reaction time is 20min, and the rotor rotating speed is 40r/min. Toluene is used as a solvent, stannous octoate is used as a catalyst, and polyoxypropylene glycol reacts with isophorone diisocyanate to prepare the linear polyurethane. 100g of graft modified ethylene propylene diene monomer, 50g of linear polyurethane, 5g of carbon black, 5g of kaolin, 3g of 2-mercaptobenzothiazole, 2g of hydrogenated vegetable oil, 15g of ammonium polyphosphate, 3g of azodicarbonamide, 0.4g of antioxidant BHT, 1g of sulfur, 0.5g of dicumyl peroxide, 2g of copper oxide and 15g of stearic acid are put into a two-roll mill, are mixed for 5min at 150 ℃, then the mixed product is placed for 12h, and is further mixed for 3min at 150 ℃, the mixed product is put on a flat vulcanizing machine, the mixed product is vulcanized under pressure at 5MPa and 150 ℃ for 5 seconds, and is foamed for 45 seconds at 150 ℃ after pressure is released to normal pressure, so as to obtain the dilatant polymer foam. The dilatant foam has a low glass transition temperature and also contains a strong dynamic hydrogen bonding effect, is dilatant at low temperature, and is prepared into a sample with a thickness of 1cm, and the impact force of the sample penetrating at 25 ℃ and-20 ℃ is 15.2KN and 16.1KN respectively according to the method of EN 1621-2012. The dilatant foam has the advantages of excellent flame retardance, insulativity, weather resistance, heat resistance, ageing resistance and the like, and can be used as a protective sleeve of electrical equipment to perform impact protection.

Example 25

In a torque rheometer, natural rubber is used as a matrix, benzoyl peroxide is used as an initiator, N-vinyl imidazole and styrene are used as grafting monomers, and a double-monomer melt grafting method is adopted to prepare modified natural rubber, wherein the mass ratio of the natural rubber to the benzoyl peroxide to the N-vinyl imidazole to the styrene is 100:0.8:15:10, the reaction temperature is 135 ℃, the reaction time is 30min, and the rotor rotating speed is 45r/min. 150g of modified natural rubber, 50g of butadiene rubber, 10g of zinc chloride, 20g of white carbon black, 15g of antimonous oxide, 30g of decabromodiphenyl ether and 8g of triallyl cyanurate are taken, mixed for 15min at 100 ℃ on a two-roll open mill, then the mixed sizing material is kept stand for 24h, the mixed sizing material is further mixed for 5min at the same temperature, the obtained tablet is pressed into a film with the thickness of 10mm at 130 ℃, and after the film is cooled, the film is placed in a 60Co gamma radiation field for irradiation for 6h at room temperature, so as to obtain the dilatant polymer elastomer. The tensile strength of the dilatant elastomer is 33.6MPa, the elongation at break is 820%, the toughness of the material is 144.5MPa, and the tearing strength is 52.5KN/m. The dilatant elastomer has good low-temperature dilatant property, is prepared into a sample with the thickness of 1cm, and can be used as a vibration damping gasket to realize damping vibration damping at room temperature and low temperature according to the method of EN1621-2012, wherein the impact force transmitted by the sample at 25 ℃ and minus 40 ℃ is 13.2KN and 13.9KN respectively.

Example 26

1 molar equivalent of ethyl hydrogen silicone oil and 10 molar equivalents of compound (a) are taken and placed in a reaction vessel, a proper amount of toluene is used for dissolution, a small amount of xylene solution of platinum (0) -1, 3-diethyl-1, 3-tetramethyl disiloxane complex (wherein the platinum content is 0.003 weight percent) is added, and the mixture is stirred and reacted for 48 hours at 60 ℃ under argon atmosphere to prepare the dynamic covalent cross-linked polysiloxane. 1 molar equivalent of ethyl hydrogen silicone oil, 12 molar equivalent of sodium styrene sulfonate and 12 molar equivalent of 2- (methacryloyloxy) ethyl trimethyl ammonium chloride are taken and placed in a reaction vessel, dissolved by a proper amount of dimethylformamide, and then a small amount of xylene solution of platinum (0) -1, 3-diethylene-1, 3-tetramethyl disiloxane complex (the platinum content is 0.003 wt%) is added, and stirred and reacted for 48 hours at 60 ℃ under argon atmosphere to obtain the supermolecule crosslinked polysiloxane. 50 parts by mass of dynamic covalent cross-linked polysiloxane, 50 parts by mass of supermolecule cross-linked polysiloxane, 40 parts by mass of polysiloxane copolymer (b), 15 parts by mass of calcium carbonate, 15 parts by mass of melamine, 5 parts by mass of carbon black, 3 parts by mass of dibutyl tin maleate, 10 parts by mass of 4-methyl-4' - (6-hydroxyhexyloxy) azobenzene and 0.5 part by mass of antioxidant 1010 are placed in an internal mixer for banburying at a banburying temperature of 100 ℃ for 25min, a discharge is taken after banburying, the materials are placed in a vacuum oven at 150 ℃ for drying for 2h, a sizing material is taken out, cooled to room temperature and placed in the internal mixer, and 1.5 parts by mass of dicumyl peroxide is added for mixing, wherein the mixing time is 10min; the rubber compound is placed on a flat vulcanizing machine for pre-vulcanizing treatment to prepare a rubber sheet with the thickness of 3mm, wherein the pressure maintaining pressure is 10MPa, the temperature maintaining temperature is 110 ℃ and the pressure maintaining time is 10min; placing the obtained rubber sheet in a high-pressure reaction kettle, firstly filling low-pressure carbon dioxide for 3min, then filling high-pressure carbon dioxide, raising the temperature of the high-pressure kettle to 50 ℃, controlling the pressure to 10MPa, and controlling the swelling and permeation time to 1h; and then rapidly releasing the pressure until the gauge pressure is 0, taking out a foaming sample, rapidly placing the foaming sample in a high-temperature blast oven for complete vulcanization treatment, wherein the temperature of the oven is 200 ℃, and the time is 2 hours, and finally obtaining the dilatant polymer foam. The dilatant foam has dilatant property in a wide temperature range, and is prepared into a sample with a thickness of 1cm, and the impact forces of the sample penetrating at 45 ℃, 25 ℃ and minus 30 ℃ are 11.2KN, 9.5KN and 11.9KN respectively according to the method of EN 1621-2012. The dilatant foam also has the characteristics of flame retardance, antibacterial property, low permanent deformation rate and the like, and can be used as a filler of a sofa, a seat and a headrest for buffering and providing comfort.

Example 27

And (2) taking 0.6 molar equivalent of hydroxyl-terminated hydrogenated polybutadiene, 0.4 molar equivalent of hydroxyl-terminated polyethylene oxide and 2 molar equivalent of compound (a), placing the materials into a reaction vessel, dissolving the materials with proper toluene, adding 6.2 molar equivalent of hexamethylene diisocyanate and a small amount of stannous octoate catalyst, stirring the materials at 60 ℃ under nitrogen atmosphere for reaction for 6 hours, adding 2 molar equivalent of carbohydrazide, continuing the reaction for 6 hours, adding 0.6 molar equivalent of pentaerythritol, continuing the reaction for 12 hours, and naturally drying the materials for 24 hours after the reaction is finished, and then drying the materials in vacuum at 90 ℃ for 6 hours to obtain the dilatant polymer elastomer. The dilatant elastomer has multiple dilatant properties and can absorb energy and protect in a wide temperature range. The dilatant elastomer also has good structural support and self-adhesion, and can be used as an anti-collision patch for anti-collision buffering.

Example 28

Toluene is used as a solvent, chloroprene rubber is used as a matrix, benzoyl peroxide is used as an initiator, a compound (a) is used as a modifier, wherein the mass ratio of the chloroprene rubber to the compound (a) is 80:4.2, and the mixture is stirred and reacted for 6 hours at 70 ℃ in a nitrogen atmosphere to prepare the dynamic covalent crosslinking modified chloroprene rubber. 150g of dynamic covalent crosslinking modified chloroprene rubber, 18g of sodium polyacrylate, 22.5g of polydiallyl dimethyl ammonium chloride, 3g of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 9g of calcium carbonate, 4.5g of carbon fiber, 4.5g of barium stearate, 12g of melamine, 3g of aluminum hydroxide, 0.6g of antioxidant 168, 6g of liquid paraffin and 12g of dioctyl phthalate are placed in an internal mixer to be internally mixed for 15min, the temperature is controlled to be 85 ℃, then the internal mixer is taken out and cooled, the internal mixer is thinned and passed 5 times, the roll gap is regulated to be 5mm, the materials are discharged, a film is cut, and finally the film is shaped and controlled to be under 10MPa in a flat vulcanizing machine, the temperature is 130 ℃ for 40min, so that the dilatant polymer elastomer is prepared. The tensile strength of the dilatant elastomer is 27.4MPa, the elongation at break is 685%, and the dilatant elastomer also has the characteristics of flame retardance, bacteriostasis and the like. When structural damage occurs to the dilatant elastomer, damage repair can be achieved by heating to 60 ℃. The dilatant elastomer has low glass transition temperature and strong dynamic ion effect, so that the dilatant elastomer has dilatant property in a wider temperature range, can be used as a buffering packaging material for shock resistance buffering, and is applied to packaging and transportation of precision instruments and valuables.

Example 29

70g of natural rubber is dissolved in toluene, 0.2g of benzoyl peroxide, 7g of compound (a) and 5.2g of compound (b) are added, after the raw materials are completely dissolved, nitrogen is introduced for 3min to remove oxygen, and then stirring reaction is carried out for 12h at 70 ℃ under nitrogen atmosphere, so that the supermolecule crosslinked natural rubber is prepared. Plasticizing 200g of supermolecule crosslinked natural rubber, 10g of carbon black and 12g of stearic acid on an open mill, sequentially adding 35g of kieselguhr, 8g of tetramethylthiuram disulfide, 8g of 4, 4-oxo-bis-benzenesulfonyl hydrazine, 10g of stearic acid, 1g of dicumyl peroxide, 6g of sulfur and 24g of naphthenic oil, thinning for 6 times, wherein the roll spacing is 1mm, the temperature is 70 ℃, the roll spacing is adjusted to be 5mm, thinning for 3 times, discharging, and cutting to obtain a mixed rubber sheet; and placing the mixed rubber sheet into a die, and performing hot-pressing foaming molding by a plate vulcanizing machine, wherein the hot-pressing temperature is 150 ℃, the vulcanizing time is 10min, and the pressure is 10MPa, so that the dilatant polymer foam is finally prepared. The dilatant foam has good low temperature resistance and does not harden when the temperature is reduced to-40 ℃; when the damage occurs, the damage repair can be realized through local heating, and the damage repair can be used as a sound insulation material to carry out noise reduction.

Example 30

Under the catalysis of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, hydroxypropyl end-capped polydimethylsiloxane with the molar ratio of 1:1.05 reacts with the compound (a) to prepare polysiloxane containing organic boric acid monoester bonds. 60 parts by mass of polyether polyol TMH-1860 (with a hydroxyl value of 180mgKOH/g and a functionality of 3), 30 parts by mass of polyether polyol TEP-565B (with a hydroxyl value of 56 mgKOH/g), 10 parts by mass of polyether polyol containing a styrene-acrylonitrile copolymer (with a hydroxyl value of about 26mgKOH/g and a functionality of 3), 2.2 parts by mass of water, 1.5 parts by mass of an organosilicon foam stabilizer, 1.8 parts by mass of a pore former Ortegol-501 and 0.8 part by mass of stannous octoate are added into a reaction vessel, and stirred uniformly to obtain a slow rebound A material, wherein the temperature of the material is controlled to be 23 ℃; taking 48 parts by mass of toluene diisocyanate to obtain a slow rebound material B, and controlling the material temperature to be 23 ℃; and adding the slow rebound material B into the slow rebound material A, stirring and mixing at 3000rpm for 6s, pouring the mixture into a mold for foaming, keeping the temperature of the mold at 55 ℃, foaming for 5min, and standing at room temperature for 72h after opening the mold to obtain the foam with slow rebound. The resulting foam was cut into two parts of the same size to give foam I and foam II, wherein foam I was immersed in a toluene solution in which polysiloxane containing organoboronic acid monoester linkages was dissolved, stirred and immersed for 24 hours, and then the foam was taken out and dried to give polysiloxane having approximately 30wt% of the polysiloxane containing organoboronic acid monoester linkages filled in the cells. Foam I and foam II were each cut into 1cm thick specimens, and foam I transmitted impact forces of 9.7KN and 10.8KN and foam II transmitted impact forces of 22.3KN and 28.5KN were measured at 25℃and-45℃respectively according to EN 1621-2012. The data show that polysiloxane filled with organic boric acid monoester bonds has very remarkable improvement on low temperature resistance of foam, and can obviously reduce the dilatancy and the sensitivity of impact resistance to temperature of the material, thereby being beneficial to keeping stable energy absorption of the material in a wider temperature range. The foam material can be used as an aviation seat cushion, a back cushion and the like for buffering, and the slow rebound resilience of the foam material can also avoid secondary injury.

Example 31

The allyl-terminated three-arm polyisobutene is prepared by active cationic polymerization with 1,3, 5-tri (2-methoxy-2-propyl) benzene as an initiator, isobutene as a monomer and allyltrimethylsilane as a quencher. And (3) putting 1 molar equivalent of the three-arm polyisobutene and 3.3 molar equivalents of the compound (a) into a reaction container, dissolving with a proper amount of dichloromethane, adding 0.01 molar equivalent of benzoin dimethyl ether, carrying out ultraviolet irradiation reaction for 1h at 365nm, and removing excessive compound (a) and other impurities after finishing the reaction to obtain the hydrogen bond crosslinked polyisobutene. 5g of tetra-isobutyl titanate and 35g of polydimethylsiloxane are taken and placed in a reaction vessel, a small amount of acetic acid aqueous solution is added, stirring and mixing are carried out for 15min, a small amount of antioxidant 168 is added, and then the temperature is raised to 110 ℃ for reaction for 5h, thus obtaining the modified polysiloxane. Taking 1 molar equivalent of three-arm polyisobutene and 1 molar equivalent of benzene-1, 3, 5-trithiol, placing the three-arm polyisobutene and the benzene-1, 3, 5-trithiol into a reaction container, recording the total mass of the reactants as 100wt%, dissolving the three-arm polyisobutene and the benzene-1, 3, 5-trithiol by using a proper amount of dichloromethane, adding 50wt% of hydrogen bond crosslinked polyisobutene, 40wt% of modified polysiloxane and 0.01 molar equivalent of benzoin dimethyl ether, stirring, swelling and mixing for 30min, then carrying out ultraviolet irradiation reaction for 1h at 365nm, and after the reaction is finished, naturally drying for 24h and then drying under reduced pressure for 12h to obtain the dilatant polymer elastomer. The dilatant elastomer has good low temperature resistance and a shape memory function, has the tensile strength of 34.1MPa, the elongation at break of 780 percent and the toughness of 140MPa, is prepared into a sample with the thickness of 1cm, and the impact forces of the sample penetrating at 25 ℃ and minus 30 ℃ are respectively 10.7KN and 12.5KN according to the method of EN 1621-2012. The dilatant elastomer also has the characteristic of low permanent deformation rate, and can be used as a buffering shoe material for buffering and absorbing energy.

Example 32

1.1 molar equivalent of mercaptopropyl-terminated polydimethylsiloxane (a), 0.5 molar equivalent of compound (b), 0.5 molar equivalent of compound (c) and 0.05 molar equivalent of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide are taken and dissolved in methylene dichloride, then the mixture is subjected to ultraviolet irradiation reaction for 3 hours at 365nm under nitrogen atmosphere, and then 0.4 molar equivalent of allyltrimethylsilane is added, and the irradiation reaction is continued for 3 hours, so that the hydrogen bond crosslinked polysiloxane is prepared. Taking 3 molar equivalents of mercaptopropyl-terminated polydimethylsiloxane (a), 1.2 molar equivalents of tripolyl amine and 0.15 molar equivalents of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, placing the components in a glass reaction container, recording the total mass of the components to be 100wt%, dissolving the components with a proper amount of dichloromethane, adding 100wt% of hydrogen bond crosslinked polysiloxane, 5wt% of liquid gallium and 2wt% of graphene, stirring, swelling and mixing for 30min, then carrying out ultraviolet irradiation reaction for 3h under a nitrogen atmosphere at 365nm, and then drying to obtain the dilatant polymer elastomer. The dilatant elastomer has dilatant and slow rebound at room temperature. The two crosslinked networks of the dilatant elastomer act synergistically to provide excellent mechanical strength, material toughness and shape memory. The dilatant elastomer also has good heat dissipation, and can be used as a protective sleeve of an industrial machine for anti-collision buffering.

Example 33

Dispersing nano silicon dioxide with the particle size of 650nm and carbon nano tubes in polyethylene glycol (with the molecular weight of 200 Da) to obtain a dilatant dispersion with the mass fraction of 78%, and filling the dilatant dispersion into polyacrylate hollow spheres to obtain the polyacrylate microspheres filled with the dilatant dispersion, wherein the filling rate is about 65%. Stannous octoate is used as a catalyst, and aminopropyl methyl siloxane-dimethyl siloxane copolymer reacts with excessive isopropyl isocyanate to prepare polysiloxane containing ureido hydrogen bond groups. 120g of brominated butyl rubber, 80g of fluororubber raw rubber and 50g of polysiloxane containing ureido hydrogen bond groups are put into a two-roll mill for mill blending, and then 10g of carbon black, 9g of mica, 8g of carbon nano tube, 10g of sulfur, 10g of zinc oxide, 4g of 2,2' -dithiodibenzothiazyl disulfide, 1.6g of tetramethylthiuram disulfide, 30g of polyacrylate microsphere filled with dilatant dispersion liquid and 4g of liquid paraffin are sequentially added, and the mixing film is obtained; placing the mixed rubber sheet on a molding press for hot press molding, cutting, and performing presulfiding in the hot press molding process to obtain a plate-shaped rubber blank with the size of 100 multiplied by 6 mm; placing the rubber blank in a foaming mold of compression molding foaming equipment, wherein the volume ratio of the cavity volume of the foaming mold to the volume of the rubber blank is 3:1, flushing carbon dioxide into the foaming mold after hydraulic mold closing, controlling the temperature in the foaming mold to be 75 ℃, controlling the pressure to be 15MPa, keeping the temperature and the pressure for 30min to enable the rubber blank to be fully swelled, releasing pressure, foaming the swelled rubber blank in the foaming mold, opening the mold after foaming is complete, and taking out the obtained pre-vulcanized rubber foaming material; and (3) placing the pre-vulcanized rubber foaming material in a thermal oven at 168 ℃ for heat preservation for 4 hours to finish the post-vulcanization process, and finally obtaining the dilatant polymer foam. The dilatant foam has a low glass transition temperature, contains strong dynamic hydrogen bonding and dilatant dispersion liquid, obtains multiple dilatant, and is prepared into a sample with the thickness of 1cm, and the impact forces of the sample penetrating at 25 ℃, 0 ℃ and minus 30 ℃ are 13.3KN, 14.7KN and 15.3KN respectively according to the method of EN1621-2012, and can be used as an anti-collision material for anti-collision and anti-collision.

Example 34

Stannous octoate is used as a catalyst, and polyoxypropylene glycol, 4 '-bis (hydroxymethyl) -2,2' -bipyridine and isophorone diisocyanate react with each other in a molar ratio of 0.8:1.2:2 to prepare the linear polyurethane containing the bidentate ligand group. 100g of ethylene-vinyl acetate copolymer, 50g of linear polyurethane containing a bidentate ligand group, 10g of compound (a), 8g of solid paraffin, 4g of stearic acid, 4g of isopropyl triisostearate titanate, 8g of polyvinyl alcohol, 5g of zinc chloride, 1.2g of dicumyl peroxide, 6g of melamine, 3g of aluminum nitride, 1.6g of nano titanium dioxide, 0.5g of antioxidant TBHQ and 0.5g of light stabilizer 770 are added into an extruder and mixed uniformly at 90 ℃ to obtain a rubber compound; then placing the mixed rubber sheet on a molding press for hot press molding, cutting, and completing presulfiding in the hot press molding process to obtain a plate-shaped rubber blank with the size of 400 multiplied by 100 multiplied by 12 mm; placing the rubber blank in a foaming mold of compression molding foaming equipment, wherein the volume ratio of the cavity volume of the foaming mold to the rubber blank is 4:1, flushing butane into the foaming mold after hydraulic mold closing, controlling the temperature in the foaming mold to be 55 ℃ and the pressure to be 6MPa, keeping the temperature and the pressure for 60min to fully swell the rubber blank, releasing pressure and opening the mold, and ejecting and foaming the swelled rubber blank to obtain pre-vulcanized rubber foam; finally, the mixture is subjected to heat preservation in a vacuum oven at 90 ℃ for 60min, and after the completion of the vulcanization and crosslinking, the dilatant polymer foam is obtained. The dilatant foam forms shrink less and no warp deformation occurs. The dilatant foam has low glass transition temperature, rich dynamic crosslinking effect, good low-temperature dilatancy, room temperature slow rebound resilience and microscopic self-repairing performance. The dilatant foam also has the characteristics of light weight, wear resistance, oil resistance, antibiosis, low permanent deformation rate and the like, and can be used as a high-grade shoe material for buffering and damping.

The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.

Claims (1)

1. The dilatant hybrid dynamic polymer is characterized by comprising vitrification dilatant, dynamic dilatant and dispersive dilatant and common covalent cross-links above gel points; the dilatant hybrid dynamic polymer also contains dynamic covalent bond and hydrogen bond action;

wherein the dynamic covalent bond is selected from the group consisting of compound (a), which has the following structure:

wherein the hydrogen bonding is formed by amino groups;

wherein, the dilatant hybrid dynamic polymer is dispersed with homopolymers with lateral groups containing amino groups and acrylate groups;

wherein the solid microparticles producing the dispersive dilatancy are selected from submicron silica, and the dispersion medium producing the dispersive dilatancy is selected from ionic liquids;

wherein the glass transition temperature of the dilatant hybrid dynamic polymer is 43 ℃;

Wherein, the form of the dilatant hybrid dynamic polymer is ionic liquid swelling gel;

wherein, the dilatant hybrid dynamic polymer is prepared by the following steps:

2-amino ethyl acrylate is used as a polymerization monomer, azodiisobutyronitrile is used as a free radical initiator, dimethyl sulfoxide is used as a solvent, and a homopolymer with amino-containing side groups is prepared through free radical polymerization; then, taking methylene dichloride as a solvent, and carrying out graft modification on the homopolymer by using acryloyl chloride, wherein the molar ratio of amino to the acryloyl chloride is 3:1, so as to prepare the homopolymer with the side group containing amino and acrylate groups;

triethylamine is used as a catalyst, methylene dichloride is used as a solvent, hydroxyl-terminated ethylene oxide-propylene oxide copolymer and succinic anhydride react for 4 hours at room temperature under stirring in nitrogen atmosphere, and then reflux reaction is carried out for 1 hour, so that the carboxyl double-terminated ethylene oxide-propylene oxide copolymer is prepared; taking 3 molar equivalents of carboxyl double-end capped ethylene oxide-propylene oxide copolymer, 1 molar equivalent of compound (a) and 2 molar equivalents of pentaerythritol, placing the copolymer and the compound (a) into a reaction vessel, dissolving the copolymer and the pentaerythritol with tetrahydrofuran, then adding 4 molar equivalents of 4-dimethylaminopyridine and 16 molar equivalents of dicyclohexylcarbodiimide, stirring the mixture at room temperature for reaction for 24 hours, and removing impurities and solvent after the reaction is finished to obtain a purified product;

15g of homopolymer with side groups containing amino groups and acrylate groups, 85g of the purified product and 20g of submicron silicon dioxide are taken and swelled in 1-hydroxyethyl-3-methylimidazole tetrafluoroborate ionic liquid, so as to obtain dilatant ionic liquid swelling gel;

after the dilatant gel is cracked and damaged, the dilatant gel is heated to 120 ℃ or irradiated by ultraviolet light to realize reversible fracture of a dynamic covalent bond, generate free radicals and initiate free radical polymerization of an acrylic ester side group, so that a novel covalent cross-linked network is obtained.