CN111378181A - Force-induced responsive polymer with single-hybrid network structure - Google Patents

Force-induced responsive polymer with single-hybrid network structure Download PDF

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CN111378181A
CN111378181A CN201910010078.4A CN201910010078A CN111378181A CN 111378181 A CN111378181 A CN 111378181A CN 201910010078 A CN201910010078 A CN 201910010078A CN 111378181 A CN111378181 A CN 111378181A
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force
covalent
crosslinking
cross
group
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不公告发明人
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Xiamen Tiance Material Technology Co ltd
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Weng Qiumei
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers

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Abstract

The invention discloses a force-responsive polymer with a single-hetero network structure, which only contains a crosslinking network, and contains covalent crosslinking and non-covalent crosslinking of a non-dynamic covalent bond, wherein the crosslinking degree of the covalent crosslinking of the non-dynamic covalent bond is above a gel point, and the crosslinking network contains at least two force-sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response. The single-hybrid network structure provides good structural stability and mechanical property for the polymer; based on the force-induced responsiveness of the force sensitive group, the detection, monitoring and warning effects on the processes of stress, deformation, damage and failure are obtained; the non-covalent dynamics of the non-covalent crosslinks may provide self-healing properties. The force-induced responsive polymer can be applied to stress induction materials, self-repairing materials, toughness materials, shape memory materials, toy materials, functional coating materials, intelligent sensors, bonding materials, plugging materials and the like.

Description

Force-induced responsive polymer with single-hybrid network structure
Technical Field
The invention relates to a force-responsive polymer and a method for realizing force-responsive response thereof, in particular to a force-responsive polymer with a single-hetero network structure and containing at least two force sensitive groups and a force-responsive method for realizing the force-responsive polymer.
Background
The polymer crosslinking is an important factor for obtaining good mechanical strength and structural stability, wherein the crosslinking effect comprises physical crosslinking and chemical crosslinking, the traditional crosslinked polymer material usually only contains a network structure in a single crosslinking form, the mechanical strength of the material can be improved to a certain extent, but the bonding effect of the polymer only containing the physical crosslinking is relatively weak, the reversibility is shown, the toughness, the tear resistance, the fatigue resistance, the self-repairing performance and the like of the material can be improved, but the reversibility of the crosslinking structure makes the material susceptible to the external environment, the performances such as acid resistance, alkali resistance, salt ion resistance, temperature resistance and the like are not good, and the stability for long-term use cannot be provided. The traditional chemical cross-linked polymer can keep higher mechanical strength and long-term use stability, but because the bonding effect of the structure of the polymer is stronger, the toughness of the material is poorer, the expansion of the material cannot be effectively prevented after silver lines/microcracks are generated in the material, and the self-repairing performance cannot be obtained after the material is damaged. In addition, the traditional cross-linked polymer material has no responsiveness to mechanical force, and can be observed and detected only when the mechanical force reaches the fracture threshold of the chemical connection structure and generates microcracks/cracks, so that the monitoring and warning effects on the stress, deformation, damage and failure processes of the material cannot be provided, and the damage to the structure cannot be effectively repaired.
Therefore, it is urgently needed to develop a polymer which has good structural stability and self-repairing performance and has specific response to mechanical force, provides effective detection, monitoring and warning effects on the processes of stress, deformation, structural damage and failure of the polymer through the force-induced responsiveness, and can perform self-repairing or self-enhancement after the polymer is damaged so as to improve the use safety of materials and prolong the service life of the materials.
Disclosure of Invention
The present invention addresses the above background by providing a force-responsive polymer having a single hetero network structure and a method for achieving a force-responsive polymer. The force-responsive polymer has a single hybrid network structure and contains at least two force-sensitive groups. The single-hybrid network structure provides good structural stability and mechanical property for the polymer; the force-induced responsive polymer has good mechanical force responsiveness, so that the polymer material can be effectively detected, monitored and warned in the processes of stress, deformation, structural damage and failure. Non-covalent interactions/cross-links in the force-responsive polymer can provide self-healing properties to the polymer and enhance the toughness properties of the material. The self-healing and/or self-enhancing properties may be achieved by one or more reactive species/groups generated by the force-responsive polymer during its force-response through chemical or physical reactions with itself or with each other or with other reactable groups or components in the system. Based on the properties, the force-induced responsive polymer can be applied to stress-induced materials, self-repairing materials, toughness materials, shape memory materials, toy materials, functional coating materials, intelligent sensors, bonding materials, plugging materials and the like.
The invention is realized by the following technical scheme:
the invention relates to a force-responsive polymer with a single-hetero network structure, which is characterized by comprising only one crosslinking network and simultaneously comprising non-dynamic covalent crosslinking and non-covalent crosslinking, wherein the crosslinking degree of the non-dynamic covalent crosslinking is above a gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response polymer with a single-hetero network structure is provided, wherein only one crosslinking network is contained, and both non-dynamic covalent crosslinking and non-covalent crosslinking are contained, and the crosslinking degree of the non-dynamic covalent crosslinking is higher than the gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
In the present invention, the force-responsive polymer has a single-hetero network structure means that the force-responsive polymer contains only one crosslinked network, wherein both non-dynamic covalent crosslinking and non-covalent crosslinking are contained, and the crosslinking degree of the non-dynamic covalent crosslinking in the crosslinked network is above the gel point. In the present invention, the crosslinked network may optionally further comprise covalent crosslinks formed by covalent moieties in the covalent force-sensitive groups having dynamic covalent character and/or the non-covalent force-sensitive groups having dynamic covalent character. The force-responsive polymer may also contain non-crosslinked components.
In a preferred embodiment of the present invention (network 1), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two force-sensitive groups.
In another preferred embodiment of the present invention (network 2), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least two covalent single force sensitive groups.
In another preferred embodiment of the present invention (network 3), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least one covalent single force sensitive group and at least one non-covalent single force sensitive group.
In another preferred embodiment of the present invention (network 4), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least one covalent single force sensitive group and at least one composite force sensitive group.
In another preferred embodiment of the present invention (network 5), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least two non-covalent single force sensitive groups.
In another preferred embodiment of the present invention (network 6), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least one non-covalent single force-sensitive group and at least one complex force-sensitive group.
In another preferred embodiment of the present invention (network 7), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two complex force sensitive groups.
In another preferred embodiment of the present invention (network 8), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two force-sensitive groups and at least one force-sensitive group is a covalent single force-sensitive group with dynamic covalent characteristics.
In another preferred embodiment of the present invention (network 9), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two covalent single force sensitive groups, and the covalent single force sensitive groups are covalent single force sensitive groups with dynamic covalent characteristics.
In another preferred embodiment of the present invention (network 10), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a non-chain-breaking covalent single force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 11), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single force sensitive groups, and at least one covalent single force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 12), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the crosslinking network contains at least one non-chain-breaking covalent single force sensitive group and at least one covalent single force sensitive group with dynamic covalent characteristics; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 13), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the crosslinking network contains at least one non-chain-breaking covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 14), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one non-chain-breaking covalent single force sensitive group and at least one composite force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 15), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single-force sensitive groups, and the covalent single-force sensitive groups are non-chain-breaking covalent single-force sensitive groups; wherein the sum of the crosslinking degrees of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 16), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network 17), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive crosslinks and non-covalent crosslinks; the crosslinking network contains at least two covalent single force sensitive groups, at least one of which is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (18 th network structure), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one dynamic covalent characteristic covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (network structure 19), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (20 th network structure), the force-responsive polymer contains only one crosslinked network containing only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single force sensitive group and at least one compound force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (21 st network structure), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single force sensitive groups, and the covalent single force sensitive groups are all covalent single force sensitive groups with chain-breaking type non-dynamic covalent characteristics; wherein the sum of the crosslinking degrees of the covalent single force sensitive group crosslinking with the chain-breaking non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (22 nd network structure), the force-responsive polymer contains only one crosslinked network containing only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one force sensitive group which is a non-chain-breaking covalent single force sensitive group and at least one chain-breaking covalent single force sensitive group with non-dynamic covalent characteristics; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, the crosslinking degree of the chain-breaking covalent non-dynamic covalent characteristic covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the two is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (23 rd network structure), the force-responsive polymer comprises only one crosslinked network, wherein common covalent, force-sensitive, and non-covalent crosslinks are present simultaneously; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point.
In another preferred embodiment of the present invention (24 th network structure), the force-responsive polymer comprises only one crosslinked network, wherein common covalent, force-sensitive, and non-covalent crosslinks are present simultaneously; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a covalent single force sensitive group with chain-breaking type non-dynamic covalent characteristics; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of the covalent single force sensitive group crosslinking with the broken chain type non-dynamic covalent characteristic is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the broken chain type non-dynamic covalent characteristic is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point.
In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo a specific chemical and/or physical change of structure under mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly undergoing a change in chemical and/or physical signal, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, free radical, catalysis, redox, addition, condensation, substitution, exchange, elimination, and so on, Decomposition, polymerization, cross-linking, coordination, hydrogen bonding, host-guest bonding, ionic bonding, change of pi-pi stacking signal/property, ionic bonding, degradation, change of viscosity signal/property, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response property/effect.
Non-covalent interactions described herein include, but are not limited to, hydrogen bonding, metal-ligand interactions, ionic interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bonding interactions, lewis acid-base pair interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic hydrogen bonding interactions, radical cation dimerization, phase separation, crystallization.
In embodiments of the invention, the force responsive polymer may have at least one glass transition temperature; the glass transition temperature may not be present; may have at least one glass transition temperature below 25 ℃.
In embodiments of the invention where the force-responsive polymer has a glass transition temperature, the glass transition temperature may be selected from the group consisting of less than 0 ℃, 0 ℃ to 25 ℃, 25 ℃ to 100 ℃, and greater than 100 ℃.
In an embodiment of the present invention, the formulation for preparing the force-responsive polymer may further comprise any one or more of the following additives or additives: auxiliary agent, filler and swelling agent. The auxiliary agent is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, sterilization and mold inhibitors, foaming agents, co-foaming agents, nucleating agents, and rheological agents; the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers; the swelling agent is selected from any one or more of the following components: water, organic solvent, ionic liquid, oligomer and plasticizer.
In the embodiment of the invention, the form of the force-responsive polymer can be common solid, gel (including hydrogel, organic gel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), elastomer, foam material and the like.
In embodiments of the invention, the force-responsive polymer may be applied to the following materials or articles: stress induction materials, self-repairing materials, toughness materials, shape memory materials, toy materials, functional coating materials, intelligent sensors, bonding materials, plugging materials and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the force-induced responsive polymer has a single-hybrid network structure, and can provide excellent structural stability and mechanical properties for a polymer material; and the mechanical force is also conducted and acted on the force sensitive group, so that the sensitivity of the force-induced responsive polymer to the mechanical force response is improved.
(2) In the present invention, the force sensitive groups in the force responsive polymer are of various types and forms, including but not limited to covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, and aggregates. Under the action of mechanical force, the force sensitive groups are stressed and activated to obtain force-induced responsiveness, so that the polymer stress, deformation, structural damage and failure processes are effectively detected, monitored and warned, and later-stage material structure optimization is facilitated. These properties are important to improve the safety of the materials, but are not available in the conventional polymer materials.
(3) Two or more force sensitive groups are combined for use, so that abundant sequential/layered, orthogonal and synergistic force-induced response performance/effects are easily obtained, and sequential color, luminescence, fluorescence/phosphorescence change, force-induced repair, force-induced crosslinking, force-induced enhancement, force-induced catalytic luminescence, force-induced catalytic crosslinking and other specific force-induced response effects are also easily obtained, which are not possessed by the existing force-induced responsive polymer system, but the specific force-induced response effect can more effectively feed back material stress information and play a role in stress monitoring and warning. The stress warning material has the advantages that the stress response effects such as force-induced crosslinking and force-induced reinforcement can be achieved, and the mechanical strength and the modulus of the material can be spontaneously improved while the stress warning effect is exerted. These properties are clearly advantageous for improving the safety of the material and prolonging the service life of the material.
(4) The force-induced responsive polymer in the invention has various non-covalent effects, which are rich in types and various in forms, including but not limited to hydrogen bond effect, metal-ligand effect, ion-dipole effect, host-guest effect, metallophilic effect, dipole-dipole effect, halogen bond effect, Lewis acid-base pair effect, cation-pi effect, anion-pi effect, benzene-fluorobenzene effect, pi-pi stacking effect, ion hydrogen bond effect, free radical cation dimerization effect, phase separation and crystallization effect, can be subjected to non-covalent element design, selection, positions and quantity in a cross-linking network and the like according to actual use requirements, can improve the mechanical strength of the polymer material, and can endow the polymer material with rich and adjustable non-covalent dynamic property and self-repairing property, meanwhile, the material has positive effects of improving the toughness and the tear resistance of the material. These rich performance characteristics are important to expand the application range of the material and prolong the service life of the material.
(5) In the invention, through reasonable design and combined use of the structure of the force sensitive group, reasonable design and combined use of the non-covalent elementary structure, selection of the polymer chain structure and design and regulation of the polymer cross-linked network structure, the force-induced responsive polymer with rich force-induced response effect and good self-repairing performance can be prepared, and the requirements of different application occasions are met.
(6) The method and the way for preparing the force-induced responsive polymer provided by the invention are various, and the auxiliary agent, the filler and the swelling agent can be added to modify the force-induced responsive polymer material according to actual needs in the preparation process, so that better processing performance, richer use performance and the like are obtained, and the application range of the polymer material is greatly widened.
These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.
Detailed Description
The present invention will be described in detail below.
The invention relates to a force-responsive polymer with a single-hetero network structure, which is characterized by comprising only one crosslinking network and simultaneously comprising non-dynamic covalent crosslinking and non-covalent crosslinking, wherein the crosslinking degree of the non-dynamic covalent crosslinking is above a gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
The invention also relates to a method for realizing force-induced response, which is characterized in that a force-induced response polymer with a single-hetero network structure is provided, wherein only one crosslinking network is contained, and both non-dynamic covalent crosslinking and non-covalent crosslinking are contained, and the crosslinking degree of the non-dynamic covalent crosslinking is higher than the gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or.
It should be noted that, in the words "group", "series", "subfamily", "class", "subclass", "species" used herein to describe various structures, the range of the group is greater than that of the series, the range of the series is greater than that of the subfamily, the range of the subfamily is greater than that of the class, the range of the class is greater than that of the subclass, and the range of the subclass is greater than that of the species, i.e., a group may have many series, a series may have many subfamilies, a subfamily may have many classes, a class may have many subclasses, and a subclass may have many varieties. Even if the force-sensitive groups and the non-covalent moieties have the same moiety structure, differences in properties may occur due to differences in the linking groups, substituents, isomers, complex structures, and the like. In the present invention, unless otherwise specified, a structure having a force-sensitive group or a noncovalent moiety having the same moiety structure but different from each other by a linker, a substituent, an isomer or the like is generally regarded as a different structure. The invention can reasonably design, select and regulate the structures of the force sensitive groups and the non-covalent elements according to the needs to obtain the optimal performance, which is also the advantage of the invention.
The term "polymerization" reaction/action as used in the present invention, unless otherwise specified, refers to a process in which a reactant of lower molecular weight forms a product of higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, or the like, i.e., a chain extension process/action other than crosslinking. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process, a branching process, a ring formation process, and the like of a reactant molecular chain other than the crosslinking process of the reactant molecular chain. In embodiments of the invention, "polymerization" includes chain growth processes resulting from covalent bonding as well as non-covalent interactions.
The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent and/or non-covalent interactions. In the crosslinking process, polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite network crosslinking, which can be regarded as a special form of polymerization. Just as a three-dimensional infinite network is reached during the crosslinking process. Therefore, the degree of crosslinking, referred to as the gel point, is also referred to as the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can constitute 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) specifically means linear, cyclic, branched, and two-dimensional, three-dimensional clusters and the like structures below the gel point and "combination" structures of the above structures.
In the present invention, the "linear" structure refers to a regular or irregular long chain linear shape of a polymer molecular chain, which is generally formed by connecting a plurality of repeating units in a continuous length, and the side groups in the polymer molecular chain generally do not exist as branched chains; for "linear structures," they are generally formed by polymerization of monomers that do not contain long chain pendant groups by polycondensation, polyaddition, ring opening, or the like.
In the present invention, the "cyclic" structure refers to the polymer molecular chain in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple ring, bridge ring, nested ring, grommet, wheel ring, etc.; as the "cyclic structure", it can be formed by intramolecular and/or intermolecular cyclization of a linear or branched polymer, and can also be produced by ring-expanding polymerization or the like.
In the present invention, the "branched" structure refers to a structure containing side chains, branched chains, and branched chains on the polymer molecular chain, including but not limited to star, H, comb, dendritic, hyperbranched, and combinations thereof, and further combinations thereof with linear and cyclic structures, such as linear chain end-linked cyclic structures, cyclic structures combined with comb structures, dendritic chain end-linked cyclic chains, and the like; for "side chain, branched chain and branched chain structures of polymer", it may have a multi-stage structure, for example, one or more stages of branches may be continued on the branches of the polymer molecular chain. As the "branched structure", there are a number of methods for its preparation, which are generally known to those skilled in the art, and which can be formed, for example, by polycondensation of monomers containing long-chain pendant groups, or by chain transfer of radicals during polyaddition, or by radiation and chemical reactions to extend branched structures out of linear molecular chains. The branched structure is further subjected to intramolecular and/or intermolecular reaction (crosslinking) to produce a cluster and a crosslinked structure.
In the present invention, the "cluster" structure refers to a two-dimensional/three-dimensional structure below the gel point generated by intramolecular and/or intermolecular reaction of polymer chains.
In the present invention, the "crosslinked" structure refers to a three-dimensional infinite network structure of a polymer.
In the present invention, the "combination type" structure refers to two or more of two-dimensional and three-dimensional clusters below linear, cyclic, branched and gel points contained in one polymer structure, for example, a cyclic chain is used as a side chain of a comb-type chain, the cyclic chain has side chains to form a cyclic comb-type chain, the cyclic chain and a straight chain form a tadpole-type chain and a dumbbell-type chain, and the combination structure of different rings, different branches, different clusters and other topological structures is also included.
In the present invention, "backbone" refers to a structure in the chain length direction of a polymer chain. For crosslinked polymers, the term "backbone" refers to any segment present in the backbone of the crosslinked network, i.e., the backbone chain in the crosslinked network that connects adjacent crosslinks. For polymers of non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most mer. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and is distributed beside the main chain; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and is arranged beside the chain. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. Unless otherwise specified, a pendant group refers specifically to groups and subgroups thereof having a molecular weight of not more than 1000Da attached to the side of the backbone of the polymer chain. When the molecular weight of the side chain, branched chain, does not exceed 1000Da, itself and the groups thereon are considered side groups. For simplicity, when the molecular weight of the side chain, branched chain, exceeds 1000Da, they are collectively referred to as side chains unless otherwise specified. The "side chain" and "side group" may have a multi-stage structure, that is, the side chain/side group may be continued to have a side chain/side group, and the side chain/side group of the side chain/side group may be continued to have a side chain/side group. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer segment may be regarded as a side chain, and the rest as a main chain.
In the present invention, the term "covalent crosslinking of a non-dynamic covalent bond" refers to covalent crosslinking by a non-dynamic covalent bond, wherein the non-dynamic covalent bond comprises a common covalent bond and a chain-breaking covalent force-sensitive group with a non-dynamic covalent characteristic. In the present invention, the term "ordinary covalent bond" refers to a covalent bond in the conventional sense, which is difficult to break at ordinary temperature (generally not higher than 100 ℃) and ordinary time (generally less than 1 day) and has no specific response to mechanical force, and includes, but is not limited to, ordinary carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc. The chain-breaking covalent force sensitive group with non-dynamic covalent characteristics refers to a chain-breaking covalent force sensitive group with non-dynamic covalent characteristics, which can be activated by force to cause chain breaking but can not be regenerated.
In the present invention, the structure and properties of the polymer can be designed and controlled by selecting and adjusting the structure of the non-dynamic covalent bond. When the non-dynamic covalent bond is a common covalent bond, the cross-linked structure is most stable; when the non-dynamic covalent bond is a non-chain-breaking covalent single force sensitive group, the covalent structure of the non-dynamic covalent bond can be changed along with the activation of the force sensitive group, but the chain breaking can not occur, so that the cross-linked structure can not be dissociated, and stress relief can be generated due to the activation of force to achieve better toughness; when the non-dynamic covalent bond is a covalent component of the non-covalent force sensitive group, the covalent structure of the non-dynamic covalent bond is not changed along with the activation of the force sensitive group, so that the force-induced activation and the stable maintenance of a cross-linked structure can be facilitated; when the non-dynamic covalent bond is a covalent single force sensitive group with chain-breaking type non-dynamic covalent characteristics, the crosslinking structure reduces the crosslinking degree along with the activation of the force sensitive group, possibly leads to dissociation, but also can improve the toughness of the material due to the activation of the force; in the invention, different properties can be realized by selecting different non-dynamic covalent bond covalent cross-links and combinations thereof, so as to achieve the ideal purpose, which is also the advantage of the invention.
In the present invention, the force-responsive polymer has a single-hetero network structure means that the force-responsive polymer contains only one crosslinked network, wherein both non-dynamic covalent crosslinking and non-covalent crosslinking are contained, and the crosslinking degree of the non-dynamic covalent crosslinking in the crosslinked network is above the gel point. In the present invention, the crosslinked network may optionally further comprise covalent crosslinks formed by covalent moieties in the covalent force-sensitive groups having dynamic covalent character and/or the non-covalent force-sensitive groups having dynamic covalent character. The force-responsive polymer may also contain non-crosslinked components.
In the present invention, the degree of crosslinking of a kind of crosslinking is not less than (inclusive of) the gel point, which means that a three-dimensional infinite network structure can be formed only by the crosslinking.
In a preferred embodiment of the present invention (network 1), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two force-sensitive groups. In this embodiment, two or more force sensitive groups can be force activated to achieve orthogonal and/or synergistic and/or sequential force-induced responsiveness. The crosslinking degree of common covalent crosslinking is above the gel point, and good mechanical properties and structural stability and mechanical strength of the material in the force-induced response process can be obtained. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 2), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least two covalent single force sensitive groups. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The covalent single force sensitive group has rich types, relatively simple structure and easy preparation. Two or more covalent single force sensitive groups are reasonably designed and combined for use, so that the force-induced responsiveness of orthogonality and/or cooperativity and/or orderliness can be obtained, the performances of force-induced catalysis, force-induced toughening, force-induced crosslinking, force-induced reinforcement and the like can be easily obtained, the use safety is greatly improved, and the service life is prolonged. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 3), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least one covalent single force sensitive group and at least one non-covalent single force sensitive group. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. Based on the difference of self activation force of the force sensitive groups, more hierarchical force-induced responsiveness is obtained, and the combination of covalent and non-covalent single force sensitive groups can obtain orthogonality and/or cooperativity force-induced responsiveness, so that the force-induced responsive polymer with the properties of force-induced color change, force-induced fluorescence/phosphorescence, force-induced catalysis, force-induced crosslinking, force-induced toughening, force-induced enhancement and the like is conveniently prepared. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 4), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least one covalent single force sensitive group and at least one composite force sensitive group. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The covalent single force sensitive structure is relatively simple and convenient to prepare, the composite force sensitive group has more flexible and various structures, the polymer structure can be more diversified, the covalent single force sensitive group and the composite force sensitive group are reasonably designed and combined for use, more abundant force-induced response effects are obtained, and the requirements of different application scenes are met. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 5), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the crosslinked network contains at least two non-covalent single force sensitive groups. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The non-covalent single force sensitive group has obvious force response effect, force response effects such as force discoloration, force fluorescence/phosphine light emission and the like are easy to obtain, and the stress magnitude of the material is easier to reflect visually by combining two or more non-covalent single force sensitive groups, so that the stress monitoring and warning are convenient. The non-covalent dynamic property of the non-covalent single force sensitive group in the cross-linking network is activated by force and the non-covalent cross-linking can obtain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 6), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least one non-covalent single force-sensitive group and at least one complex force-sensitive group. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The non-covalent single force sensitive group has obvious force response effect, the composite force sensitive group has more flexible and diversified structures, the non-covalent single force sensitive group and the composite force sensitive group are reasonably designed and combined for use, the orthogonality and/or the cooperativity can be obtained, and the stress size difference and the stress monitoring and warning of the material can be more easily fed back. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 7), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two complex force sensitive groups. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The flexibility and the diversity of the composite force sensitive groups can provide flexible and diverse polymer structures, and various composite force sensitive groups are combined for use, so that richer force-induced responsiveness can be obtained, and the requirements of special application scenes can be met. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 8), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two force-sensitive groups and at least one force-sensitive group is a covalent single force-sensitive group with dynamic covalent characteristics. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. The covalent single force sensitive groups with dynamic covalent characteristics can be regenerated, and multiple and recyclable force-induced responsiveness can be obtained. Based on the reversible characteristic of covalent single force sensitive groups with dynamic covalent characteristics and non-covalent crosslinking, certain self-repairing performance and shape memory function can be obtained.
In another preferred embodiment of the present invention (network 9), the force-responsive polymer comprises only one crosslinked network, wherein both the common covalent crosslinks and the non-covalent crosslinks are present, wherein the common covalent crosslinks have a degree of crosslinking above the gel point and the non-covalent crosslinks have a degree of crosslinking above or below the gel point; the cross-linked network contains at least two covalent single force sensitive groups, and the covalent single force sensitive groups are covalent single force sensitive groups with dynamic covalent characteristics. In the embodiment, the crosslinking degree of common covalent crosslinking is more than the gel point, so that the structural stability of the polymer before and after force-induced response can be provided, and the mechanical strength is prevented from being greatly reduced after force-induced activation. Orthogonal and/or synergistic force-induced responsiveness may be obtained using two or more force-sensitive groups in combination. The force sensitive groups in the cross-linked network are covalent single force sensitive groups with dynamic covalent characteristics, and completely reversible, multiple and recyclable force sensitive response effects can be obtained based on reversible force sensitive response characteristics. Based on the reversible characteristic of the force sensitive groups and the non-covalent crosslinking, certain self-repairing performance and shape memory function can be obtained.
In another preferred embodiment of the present invention (network 10), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a non-chain-breaking covalent single force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristic of the force sensitive group without chain scission, the disintegration of a cross-linked network and the sharp reduction of mechanical strength in the force-induced response process can be avoided, and the toughness of the material can be increased. Orthogonal and/or synergistic and/or sequential force-induced responsiveness can be achieved using at least two force-sensitive groups in combination. The non-covalent crosslinking provides non-covalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 11), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single force sensitive groups, and at least one covalent single force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristic of the force sensitive group without chain scission, the disintegration of a cross-linked network and the sharp reduction of mechanical strength in the force-induced response process can be avoided, and the toughness of the material can be increased. The covalent single force sensitive group has rich types, relatively simple structure and easy preparation. Different covalent single force sensitive groups are reasonably designed and combined for use, so that the force-induced responsiveness of orthogonality and/or cooperativity and/or orderliness can be obtained, the performances of force-induced catalysis, force-induced toughening, force-induced crosslinking, force-induced reinforcement and the like can be easily obtained, the use safety of the material is greatly improved, and the service life of the material is greatly prolonged. The non-covalent crosslinking provides non-covalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 12), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the crosslinking network contains at least one non-chain-breaking covalent single force sensitive group and at least one covalent single force sensitive group with dynamic covalent characteristics; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristic of the force sensitive group without chain scission, the disintegration of a cross-linked network and the sharp reduction of mechanical strength in the force-induced response process can be avoided, and the toughness of the material can be increased. The covalent single force sensitive group with dynamic covalent character can be regenerated, which is beneficial to obtain multiple and recyclable force responsiveness. Based on the reversible characteristic of covalent single force sensitive groups with dynamic covalent characteristics and non-covalent crosslinking, certain self-repairing performance can be obtained, and the shape memory function and the super toughness can be obtained.
In another preferred embodiment of the present invention (network 13), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the crosslinking network contains at least one non-chain-breaking covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristic of the force sensitive groups without chain scission, the disintegration of a cross-linked network and the sharp reduction of mechanical strength in the force-induced response process can be avoided. The non-covalent single force sensitive group has obvious force response effect, is easy to obtain force response effects such as force discoloration, force fluorescence/phosphine light emission and the like, and is easy to visually monitor and warn the stress of the material. Based on the reversible characteristic of non-covalent single force sensitive groups and non-covalent crosslinking, certain self-repairing performance and improved toughness can be obtained.
In another preferred embodiment of the present invention (network 14), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one non-chain-breaking covalent single force sensitive group and at least one composite force sensitive group; wherein the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristic of the force sensitive groups without chain scission, the disintegration of a cross-linked network and the sharp reduction of mechanical strength in the force-induced response process can be avoided. The flexibility and diversity of the composite force sensitive groups can provide flexible and diverse polymer structures, and the non-chain-breaking covalent single force sensitive groups and the composite force sensitive groups are combined for use, so that more orthogonal or synergistic force-induced responsiveness can be obtained, and the requirements of different application scenes are met. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 15), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single-force sensitive groups, and the covalent single-force sensitive groups are non-chain-breaking covalent single-force sensitive groups; wherein the sum of the crosslinking degrees of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. The force sensitive groups in the cross-linked network have the characteristic of non-chain-breaking force response, and can avoid the disintegration of the cross-linked network and the sharp reduction of the mechanical strength in the force-induced response process. The combination use of at least two covalent single force sensitive groups can obtain orthogonal and/or synergistic force-induced responsiveness, can conveniently obtain sequential changes of color, fluorescence and the like based on the difference of the activation force of the force sensitive groups, and can better feed back, monitor and warn the stress state and overload information of materials. The non-covalent cross-linking is used as the supplement of structural stability and mechanical strength, provides non-covalent dynamic property, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 16), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristics of the broken chain and the non-dynamic covalent characteristics of the force sensitive group, the material is favorably degraded and the toughness is improved. Orthogonal and/or synergistic and/or sequential force-induced responsiveness can be achieved using a combination of at least two or more force-sensitive groups. The non-covalent crosslinking provides non-covalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (network 17), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive crosslinks and non-covalent crosslinks; the crosslinking network contains at least two covalent single force sensitive groups, at least one of which is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since there is no ordinary covalent crosslinking in the structure and the crosslinking degree of the force-sensitive group crosslinking is above the gel point, a sensitive force-responsiveness can be obtained; based on the force response characteristics of the broken chain and the non-dynamic covalent characteristics of the force sensitive group, the material is favorably degraded and the toughness is improved. The covalent single force sensitive groups have relatively simple structure and rich force response performance, and orthogonal and/or synergistic force-induced responsiveness can be obtained by combining and using different covalent single force sensitive groups. The non-covalent crosslinking provides non-covalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (18 th network structure), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one dynamic covalent characteristic covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. When one force sensitive group in the cross-linked network is stressed and activated, the total cross-linking degree of the network is reduced, the force-induced activation process of other covalent single force sensitive groups in the network is accelerated, sequential force-induced responsiveness is obtained, and based on the chain breaking force-induced response characteristics of the force sensitive groups, better force-induced degradation performance can be obtained, and meanwhile, the method has a positive effect on improving the toughness of the material. Based on the reversible characteristic of covalent single force sensitive groups with dynamic covalent characteristics and non-covalent crosslinking, certain self-repairing performance can be obtained.
In another preferred embodiment of the present invention (network structure 19), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. When one force sensitive group in the cross-linked network is stressed and activated, the total cross-linking degree of the network is reduced, the force activation process of other force sensitive groups in the network is accelerated, sequential force-induced responsiveness is obtained, and meanwhile, the toughness and the degradation performance of the material are improved. Based on the reversible characteristic of non-covalent single force sensitive groups and non-covalent cross-linking, certain self-repairing performance can be obtained.
In another preferred embodiment of the present invention (20 th network structure), the force-responsive polymer contains only one crosslinked network containing only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single force sensitive group and at least one compound force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. The covalent single force sensitive group has a relatively simple structure, the composite force sensitive group has a flexible structure, and the combination of the covalent single force sensitive group and the composite force sensitive group can obtain richer force-induced responsiveness and meet the requirements of different application scenes. And the noncovalent crosslinking in the crosslinking network provides noncovalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (21 st network structure), the force-responsive polymer comprises only one crosslinked network comprising only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least two covalent single force sensitive groups, and the covalent single force sensitive groups are all covalent single force sensitive groups with chain-breaking type non-dynamic covalent characteristics; wherein the sum of the crosslinking degrees of the covalent single force sensitive group crosslinking with the chain-breaking non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. The force sensitive groups in the cross-linked network are all covalent single force sensitive groups with chain-breaking type non-dynamic covalent characteristics, when one of the force sensitive groups is stressed and activated, the total cross-linking degree of the network is reduced, the force activation process of other force sensitive groups in the network is accelerated, the change of sequential color, fluorescence and luminescence properties is convenient to obtain, and material stress and overload information is better fed back, monitored and warned.
In another preferred embodiment of the present invention (22 nd network structure), the force-responsive polymer contains only one crosslinked network containing only force-sensitive group crosslinks and non-covalent crosslinks; the cross-linked network contains at least one force sensitive group which is a non-chain-breaking covalent single force sensitive group and at least one chain-breaking covalent single force sensitive group with non-dynamic covalent characteristics; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, the crosslinking degree of the chain-breaking covalent non-dynamic covalent characteristic covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the two is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point. In this embodiment, since no ordinary covalent crosslinking is present in the structure and the degree of crosslinking of the force sensitive group crosslinks is above the gel point, a sensitive force responsiveness can be obtained. The covalent single-force sensitive groups with the non-chain-breaking covalent single-force sensitive groups and the chain-breaking non-dynamic covalent characteristics are used in combination, so that the orthogonal and/or synergistic force-induced responsiveness is obtained, the complete disintegration of a cross-linked network is avoided while the toughness of the material is improved on the basis of respective force-induced response characteristics, and the mechanical strength is prevented from being rapidly reduced after force-induced activation. The non-covalent crosslinking provides non-covalent dynamics, and can obtain certain self-repairing performance and improve the toughness of the material.
In another preferred embodiment of the present invention (23 rd network structure), the force-responsive polymer comprises only one crosslinked network, wherein common covalent, force-sensitive, and non-covalent crosslinks are present simultaneously; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point. The network structure can well balance the mechanical strength, the structural stability and the sensitivity of force response. Orthogonal and/or synergistic and/or sequential force-induced responsiveness can be achieved using at least two force-sensitive groups in combination. The non-covalent crosslinking provides non-covalent dynamics and can obtain certain self-repairing performance.
In another preferred embodiment of the present invention (24 th network structure), the force-responsive polymer comprises only one crosslinked network, wherein common covalent, force-sensitive, and non-covalent crosslinks are present simultaneously; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a covalent single force sensitive group with chain-breaking type non-dynamic covalent characteristics; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of the covalent single force sensitive group crosslinking with the broken chain type non-dynamic covalent characteristic is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the broken chain type non-dynamic covalent characteristic is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point. The network structure can well balance the mechanical strength, the sensitivity of force response and the force-induced degradation performance. Orthogonal and/or synergistic and/or sequential force-induced responsiveness can be achieved using at least two force-sensitive groups in combination. Non-covalent crosslinking provides non-covalent dynamics and self-healing properties.
The present invention can be variously modified in addition to the preferred embodiments described above. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.
In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo a specific chemical and/or physical change of structure under mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly undergoing a change in chemical and/or physical signal, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, free radical, catalysis, redox, addition, condensation, substitution, exchange, elimination, and so on, Decomposition, polymerization, cross-linking, coordination, hydrogen bonding, host-guest bonding, ionic bonding, change of pi-pi stacking signal/property, ionic bonding, degradation, change of viscosity signal/property, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response property/effect.
In the present invention, the force-sensitive moiety includes covalent type and non-covalent type. Wherein, the covalent type force sensitive element is mainly related to chemical changes such as breaking, eliminating, bonding, isomerization and the like of covalent bonds under the action of mechanical force, and comprises but not limited to homolytic cleavage, heterolytic cleavage, reverse cyclization, electrocyclic ring opening, bending activation, elimination, addition, isomerization and the like; the non-covalent force sensitive element mainly relates to physical changes such as dissociation of a supramolecular complex, disassembly and assembly of an assembly body, separation of a composition, separation of an aggregate and the like under the action of mechanical force.
In the present invention, the mechanical force source includes, but is not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling, bending, twisting, i.e. the force-induced response is obtained by providing a mechanical force including, but not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling, bending, twisting.
In the present invention, the force sensitive groups include single force sensitive groups and complex force sensitive groups. Wherein the single force-sensitive moiety comprises only one force-sensitive element or only one force-sensitive element in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-responsive signal, comprising both covalent single force-sensitive moieties and non-covalent single force-sensitive moieties. Wherein, the composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and includes but not limited to tying structures, gating structures, parallel structures, tandem structures, and two or more of tying, gating, parallel and tandem structures, and multi-composite structures formed by multi-stage combination of the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
In the present invention, even if the force-sensitive groups have the same structure of force-sensitive moiety, differences in their properties may be caused due to differences in the linker, substituent, isomer, complex structure, etc. In the present invention, unless otherwise specified, force-sensitive groups having the same structure of force-sensitive moiety but different structures due to a linker, a substituent, an isomer, a complex structure, and the like are regarded as different structures.
In the present invention, the force-responsive polymer comprises at least two force-sensitive groups, which may be at least two different types of force-sensitive groups, or at least two different subclasses of force-sensitive groups, or at least two different types of force-sensitive groups, or at least two different subseries of force-sensitive groups, or at least two different series of force-sensitive groups, or at least two different groups of force-sensitive groups. The invention can reasonably design, select, regulate and combine the force-sensitive groups according to the needs to obtain the best performance, which is also the advantage of the invention.
In the present invention, the division is made by a force-activated reaction mechanism, and the covalent single force sensitive groups include, but are not limited to, the following groups: covalent single-force sensitive groups based on homolytic mechanism, covalent single-force sensitive groups based on heterolytic mechanism, covalent single-force sensitive groups based on reverse cyclization mechanism, covalent single-force sensitive groups based on electrocyclization mechanism, covalent single-force sensitive groups based on flexural activation mechanism, and covalent single-force sensitive groups based on other mechanisms.
In the present invention, covalent single force sensitive groups based on the homolytic mechanism include, but are not limited to, the following series: peroxide series, disulfo/polysulfide series, diselenide/polyselenide series, azonitrile series, bisarylfuranone series, bisarylcyclic ketone series, bisarylcyclopentenedione series, bisarylchromene series, arylbiimidazole series, arylethane series, dicyanotetrarylethane series, arylpinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane-substituted ethane series, bifluorene series, allylsulfide series, thio/seleno ester series covalent monomelic groups.
In the invention, the covalent single force-sensitive group of the peroxide series homolysis mechanism refers to a force-sensitive group containing a peroxide force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000121
wherein the content of the first and second substances,
Figure BDA0001936065950000122
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000123
wherein the content of the first and second substances,
Figure BDA0001936065950000124
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the disulfide/polysulfide series homolytic mechanism refers to a force-sensitive group containing disulfide/polysulfide force-sensitive elements, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0001936065950000125
wherein m is the number of sulfur atoms connected by a single bond, and the value of m is a certain specific integer value of more than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;
wherein the content of the first and second substances,
Figure BDA0001936065950000131
indicates that n is connected with
Figure BDA0001936065950000132
An aromatic ring of (2); wherein the value of n is 0, 1 or an integer greater than 1; the symbols are the sites connected with other structures in the formula, and if not specifically noted, the symbols appearing hereinafter have the same meaning and are not repeated; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions
Figure BDA0001936065950000133
Are the same or different; in order to increase the conjugation effect and the steric hindrance, promote the homolytic fracture of the force sensitive group under the action of the mechanical force, facilitate the stabilization of the formed free radical and obtain the reversible force-activated characteristic,
Figure BDA0001936065950000134
preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950000135
said
Figure BDA0001936065950000136
Further preferred is at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0001936065950000137
wherein L is1Are divalent linking groups, each independently selected from, but not limited to:
Figure BDA0001936065950000138
l in different positions1Are the same or different; wherein L is2Are divalent linking groups, each independently selected from, but not limited to: a direct bond,
Figure BDA0001936065950000139
Figure BDA00019360659500001310
L in different positions2Are the same or different;
wherein R is1、R2、R3、R4Each independently selected from any suitable atom (including hydrogen atoms), substituent; the substituent contains a heteroatom or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, R1、R2、R3、R4Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl radical, C1-20Heterohydrocarbyl, substituted C1-20Hydrocarbyl or substituted C1-20Heterohydrocarbyl, and combinations of two or more of the foregoing. In order to increase the steric hindrance of nitrogen atoms in the force-sensitive groups, promote the homolytic cleavage of the force-sensitive groups under the action of mechanical force and facilitate the stabilization of the formed free radicalsAnd promote the coupling of said radicals or the reversible exchange of force-sensitive groups, obtaining good reversible properties, R1、R2、R3、R4Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C1-20Alkyl radical, C1-20Heteroalkyl, cyclic structure C1-20Alkyl, C of cyclic structure1-20Heteroalkyl group, C1-20Aryl radical, C1-20A heteroaryl group; in general terms, the structures in the general formulae 1-B-5, 1-B-7
Figure BDA0001936065950000141
Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950000142
said
Figure BDA0001936065950000143
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0001936065950000144
wherein the content of the first and second substances,
Figure BDA0001936065950000145
is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one of the ring-forming atoms of the aliphatic ring is a nitrogen atom, the rest of the ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms, and hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein the content of the first and second substances,
Figure BDA0001936065950000146
indicates that n is connected with
Figure BDA0001936065950000147
Wherein n is 0, 1 or an integer greater than 1; in order to increase the steric hindrance of the nitrogen atom in the force-sensitive group, promote homolytic cleavage of the force-sensitive group under the action of mechanical forces, facilitate stabilization of the free radicals formed, and promote coupling of said free radicals
Figure BDA0001936065950000148
Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950000149
said
Figure BDA00019360659500001410
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA00019360659500001411
Figure BDA0001936065950000151
wherein the content of the first and second substances,
Figure BDA0001936065950000152
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation. It is to be expressly noted that, when in a structure "
Figure BDA0001936065950000153
Each independently associated with any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activationOr the force sensitive group containing the structure has at least one activatable bond on each of the left and right sides
Figure BDA0001936065950000154
With substituted or supramolecular polymer chains participating in force activation, the force being transmitted through these chains
Figure BDA0001936065950000155
Acting on the force sensitive groups, wherein the included angle formed by the acting forces on the left side and the right side is not higher than 180 degrees, and preferably smaller than 180 degrees; unless otherwise indicated, appear hereinafter "
Figure BDA0001936065950000156
Each independently linked to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation "have the same meaning and are not repeated.
Typical structures of the general formulae 1-B-1 to 1-B-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000157
wherein the content of the first and second substances,
Figure BDA0001936065950000158
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structures of the formulae 1-B-1 to 1-B-7 may be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000159
Figure BDA0001936065950000161
wherein the content of the first and second substances,
Figure BDA0001936065950000162
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the diselenide/polyselene series homolysis mechanism refers to a force sensitive group containing diselenide/polyselene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:
Figure BDA0001936065950000163
wherein m is the number of selenium atoms connected by a single bond, and the value of m is a certain specific integer value greater than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein the content of the first and second substances,
Figure BDA0001936065950000164
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein R is1、R2、R3、R4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5; wherein the content of the first and second substances,
Figure BDA0001936065950000165
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;
Figure BDA0001936065950000166
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae 1-C-1 to 1-C-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000171
wherein the content of the first and second substances,
Figure BDA0001936065950000172
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, typical structures of the formulae 1-C-1 to 1-C-7 may be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000173
Figure BDA0001936065950000181
wherein the content of the first and second substances,
Figure BDA0001936065950000182
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the azonitrile series homolytic mechanism refers to a force sensitive group containing azonitrile force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000183
wherein R is5、R6、R7、R8Each independently selected from, but not limited to, a hydrogen atom, a halogen atom, a heteroatom group, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl groups, and combinations of two or more of the foregoing, preferably selected from hydrogen atoms, halogen atoms, C1-20Alkyl radical, C1-20Heteroalkyl group, more preferably selected from hydrogen atom, C1-5Alkyl radical, C1-5Heteroalkyl, more preferably selected from cyano, methyl, ethyl, propyl, butyl;
Figure BDA0001936065950000184
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-D-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000185
wherein the content of the first and second substances,
Figure BDA0001936065950000186
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bisaryl furanone series homolytic mechanism refers to a force sensitive group containing bisaryl furanone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000187
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w1Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0001936065950000188
Figure BDA0001936065950000189
Is preferably selected from
Figure BDA00019360659500001810
Figure BDA00019360659500001811
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA00019360659500001812
With or without looping.
Wherein the structure represented by formula 1-E-1 is preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500001813
wherein each G is independently selected from
Figure BDA00019360659500001814
Said
Figure BDA00019360659500001815
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein, W, W1、
Figure BDA00019360659500001816
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1;
wherein the content of the first and second substances,
Figure BDA0001936065950000191
to be connected with n
Figure BDA0001936065950000192
An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group; at different positions in the same general formula
Figure BDA0001936065950000193
Are the same or different; by way of example, the
Figure BDA0001936065950000194
At least one of the following structures can be selected, but the present invention is not limited to the aboveThe method is limited to the following steps:
Figure BDA0001936065950000195
said
Figure BDA0001936065950000196
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0001936065950000197
wherein L is1、L2The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
A typical structure of the formula 1-E-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000198
wherein, W, W1、
Figure BDA0001936065950000199
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-E-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000201
wherein, W, W1The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000202
independently of one another and participating in force activationPolymer chains or supramolecular polymer chains.
In the invention, the covalent single force sensitive group of the biaryl cyclic ketone series homolysis mechanism refers to a force sensitive group containing biaryl cyclic ketone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000203
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w2Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0001936065950000204
Figure BDA0001936065950000205
Is preferably selected from
Figure BDA0001936065950000206
Figure BDA0001936065950000207
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0001936065950000208
With or without looping.
Wherein the structure represented by formula 1-F-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000209
wherein, W, W2、
Figure BDA00019360659500002010
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00019360659500002011
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-F-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000211
wherein, W, W2、
Figure BDA0001936065950000212
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-F-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000213
wherein, W, W2、
Figure BDA0001936065950000214
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000215
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the diarylcyclopentenedione series homolytic mechanism refers to a force sensitive group containing diarylcyclopentenedione force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:
Figure BDA0001936065950000216
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;
Figure BDA0001936065950000221
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0001936065950000222
With or without looping.
Wherein the structure represented by formula 1-G-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000223
wherein, W,
Figure BDA0001936065950000224
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA0001936065950000225
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-G-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000226
wherein, W,
Figure BDA0001936065950000227
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the general formula 1-G-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000228
wherein, the definition, the selection range and the preferable range of W are the same as those of the general formula 1-G-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000231
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bisaryl chromene series homolytic mechanism refers to a force sensitive group containing bisaryl chromene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000232
wherein, W3Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0001936065950000233
Is preferably selected from
Figure BDA0001936065950000234
V, V' are each independently selected from carbon atoms, nitrogen atoms; when V, V 'is a nitrogen atom, V, V' is linked to
Figure BDA0001936065950000235
Is absent;
Figure BDA0001936065950000236
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0001936065950000237
Form a ring or notAnd (4) a ring.
Wherein the structure represented by formula 1-H-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000238
wherein, W3、V、V’、
Figure BDA0001936065950000239
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1;
Figure BDA00019360659500002310
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
Among them, the structure represented by the general formula 1-H-1 further preferably has a structure represented by the following formula:
Figure BDA00019360659500002311
wherein, W3、V、V’、
Figure BDA00019360659500002312
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00019360659500002313
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-H-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000241
wherein, W3、
Figure BDA0001936065950000242
Definition, selection range, preferred range ofThe same as 1-H-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-H-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000243
Figure BDA0001936065950000251
wherein, W3The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000252
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl biimidazole series homolytic mechanism refers to a force sensitive group containing aryl biimidazole force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000253
wherein the content of the first and second substances,
Figure BDA0001936065950000254
represents that the ring has a conjugated structure; wherein the content of the first and second substances,
Figure BDA0001936065950000255
is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,
Figure BDA0001936065950000256
the two five-membered nitrogen heterocycles form a carbon-carbon single bond and carbon between each two ring-forming atomsNitrogen single bond or polycyclic structure formed by nitrogen-nitrogen single bond; according to different
Figure BDA0001936065950000257
The linkage, formula 1-I-1 includes but is not limited to one or more of the following isomers:
Figure BDA0001936065950000258
Figure BDA0001936065950000259
it should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs are regarded as the same structural motif in the present invention;
Figure BDA00019360659500002510
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA00019360659500002511
With or without looping.
Wherein the structure represented by the general formula 1-I-1 is preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500002512
wherein the content of the first and second substances,
Figure BDA00019360659500002513
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00019360659500002514
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
The typical structure of the formula 1-I-1 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500002515
wherein the content of the first and second substances,
Figure BDA00019360659500002516
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the general formula 1-I-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000261
wherein L is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000262
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl ethane series homolysis mechanism refers to a force sensitive group containing aryl ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000263
wherein R is2Each independently selected from any suitable atom (including a hydrogen atom), substituent selected from hydroxy, phenyl, phenoxy, C, and substituted polymer chain with or without participation in force activation1-10Alkyl radical, C1-10Alkoxy radical, C1-10Alkoxyacyl group, C1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein the content of the first and second substances,
Figure BDA0001936065950000271
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA0001936065950000272
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-J-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000273
wherein R is2The definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000274
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the dicyano tetraarylethane series homolysis mechanism refers to a force sensitive group containing dicyano tetraarylethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000275
wherein the content of the first and second substances,
Figure BDA0001936065950000276
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA0001936065950000277
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-K-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000278
Figure BDA0001936065950000281
wherein L is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000282
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl pinacol series homolysis mechanism refers to a force sensitive group containing an aryl pinacol force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000283
wherein, W4Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,
Figure BDA0001936065950000284
Preferably from a direct bond,
Figure BDA0001936065950000285
Figure BDA0001936065950000286
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-L-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000287
wherein, W4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1;
Figure BDA0001936065950000288
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the chain transfer series homolytic mechanism refers to a force-sensitive group containing a chain transfer force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0001936065950000289
wherein R is2And
Figure BDA0001936065950000291
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; w4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1; r1、R2、R3、R4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5;
Figure BDA0001936065950000292
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;
wherein R is1Each independently selected from atoms (including hydrogen atoms), substituents, R at different positions1Are the same or different in structure; wherein the substituent contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R1Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl and groups of two or more of the aboveAnd (c) synthesizing the resulting substituent. In order to promote the homolytic fracture of the force sensitive group under the action of mechanical force, increase the oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate the coupling of the further free radical or participate in other free radical reactions, and obtain the reversible force-induced activation characteristic, the self-repairing performance and the self-enhancing performance, R1Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene1-20Hydrocarbyl/heterohydrocarbyl; r1Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;
wherein, V3Selected from tellurium atoms, antimony atoms, bismuth atoms; wherein k is and V3Connected to each other
Figure BDA0001936065950000293
The number of (2); when V is3In the case of tellurium atoms, k is 1, meaning that there is only one
Figure BDA0001936065950000294
And V3Connecting; when V is3When it is an antimony atom or a bismuth atom, k is 2, which means that there are two
Figure BDA0001936065950000295
And V3Are connected with two
Figure BDA0001936065950000296
Are the same or different in structure;
wherein, L 'is a divalent linking group, and the structures of L' at different positions are the same or different; wherein the divalent linking group contains a hetero atom or does not contain a hetero atom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, and the structure is not particularly limitedThe cyclic structure includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, each of said L' is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. In order to promote homolytic cleavage of the force sensitive group under the action of mechanical force, increase oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate further coupling of the free radical or participate in other free radical reactions, and obtain reversible force-induced activation property, self-repairing property and self-enhancing property, L' is respectively and independently preferably selected from acyl, acyloxy, acylthio, acylamino, oxyacyl, sulfuryl, phenylene and divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group1To the carbon atom(s) of (a);
in general terms, of the formulae 1-M-1 to 1-M-8
Figure BDA0001936065950000297
Preferably, the present invention is not limited to one selected from the following structures:
Figure BDA0001936065950000298
wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein R represents the number of R connected with a benzene ring, and the value of R is an integer selected from 0 to 5; wherein m is the number of repeating units, which can be a fixed value or an average value;
said
Figure BDA0001936065950000299
Further preferred is at least one of the following structures, but the present invention is not limited thereto:
Figure BDA00019360659500002910
Figure BDA0001936065950000301
wherein, the definitions, selection ranges and preferred ranges of R, R and m are as described in the primary structure;
wherein the content of the first and second substances,
Figure BDA0001936065950000302
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-M-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000303
wherein R is2The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-1;
Figure BDA0001936065950000304
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 1-M-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000305
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-2;
Figure BDA0001936065950000306
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000307
wherein, W4The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-3;
Figure BDA0001936065950000308
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000309
Figure BDA0001936065950000311
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-4;
Figure BDA0001936065950000312
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000313
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-5;
Figure BDA0001936065950000314
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-6 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000315
Figure BDA0001936065950000321
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-6;
Figure BDA0001936065950000322
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000323
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-7;
Figure BDA0001936065950000324
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the formulae 1 to M-8 may be illustrated below, but the present invention is not limited thereto:
Figure BDA0001936065950000325
Figure BDA0001936065950000331
wherein m is defined and selectedThe range, preferably the range is the same as that of the general formula 1-M-8;
Figure BDA0001936065950000332
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the cyclohexadienone series homolytic mechanism refers to a force sensitive group containing cyclohexadienone force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:
Figure BDA0001936065950000333
wherein the content of the first and second substances,
Figure BDA0001936065950000334
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4;
Figure BDA0001936065950000335
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae 1-N-1 to 1-N-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000336
wherein the content of the first and second substances,
Figure BDA0001936065950000337
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the tetracyanoethane series homolysis mechanism refers to a force sensitive group containing tetracyanoethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000341
wherein the content of the first and second substances,
Figure BDA0001936065950000342
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 1-O-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000343
wherein the content of the first and second substances,
Figure BDA0001936065950000344
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3;
Figure BDA0001936065950000345
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of formula 1-O-1 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000346
wherein L is1The definitions, selection ranges, preferred ranges of (a) are as described in the preceding sections of this series;
Figure BDA0001936065950000351
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the cyanoacyl ethane series homolysis mechanism refers to a force-sensitive group containing cyanoacyl ethane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0001936065950000352
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein, W5Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,
Figure BDA0001936065950000353
Is preferably selected from
Figure BDA0001936065950000354
Figure BDA0001936065950000355
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0001936065950000356
With or without looping.
Wherein the structure represented by formula 1-P-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000357
wherein, W, W5、
Figure BDA0001936065950000358
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-P-1.
A typical structure of the formula 1-P-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000359
wherein the content of the first and second substances,
Figure BDA00019360659500003510
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the adamantane substituted ethane series homolytic mechanism refers to a force sensitive group containing adamantane substituted ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA00019360659500003511
wherein Ad is selected from the group consisting of bivalent or multivalent adamantyl and dimeric or multimeric derivatives thereof; by way of example, the Ad is selected from, but not limited to:
Figure BDA00019360659500003512
wherein the content of the first and second substances,
Figure BDA00019360659500003513
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-Q-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500003514
wherein the content of the first and second substances,
Figure BDA00019360659500003515
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bifluorene series homolysis mechanism refers to a force sensitive group containing bifluorene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000361
wherein R is3Each independently selected from cyano, C1-10Alkoxy radicalAcyl radical, C1-10Alkyl acyl radical, C1-10An alkylaminoacyl group, a phenyl group, a substituted phenyl group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, wherein the substituent atom or the substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbon group substituent group, and a heteroatom-containing substituent group; wherein the content of the first and second substances,
Figure BDA0001936065950000362
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formula 1-R-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000363
wherein the content of the first and second substances,
Figure BDA0001936065950000364
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the homolytic mechanism of the allyl sulfide series refers to a force-sensitive group containing allyl sulfide force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000365
wherein, C1、C2、C3Represents carbon atoms, and the numbers at the upper right corner of the carbon atoms are used for distinguishing carbon atoms at different positions so as to facilitate the accuracy and the conciseness of description;
wherein R is1 1、R1 2、R1 3、R1 4Each independently selected from atoms (including hydrogen atoms), substituents; r1 1、R1 2、R1 3、R1 4Each independently preferably selected from hydrogen atomsHalogen atom, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20A hydrocarbon group/heterohydrocarbon group, the substituent atom or substituent group being not particularly limited; r1 1、R1 2、R1 3、R1 4Each independently more preferably from a hydrogen atom, a halogen atom, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heterohydrocarbyl radical, C1-20Hydrocarbyloxyacyl group, C1-20Hydrocarbyl thioacyl, C1-20Hydrocarbyl aminoacyl groups and substituents formed from combinations of two or more of the above groups; r1 1、R1 2、R1 3、R1 4Each independently of the others is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl;
wherein Z is2Is a divalent linking atom or a divalent linking group; when Z is2When selected from divalent linking atoms, it is selected from S atoms; when Z is2When the divalent linking group is selected, the divalent linking group contains a hetero atom or does not contain a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10; the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure or a cyclic structure; the cyclic structure is selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, Z2Selected from, but not limited to, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed by a hydrocarbyl/heterohydrocarbyl group and a combination of two or more of the above groups, wherein the substituent atom or substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbyl substituent group, and a heteroatom-containing substituent group; z2More preferably divalent acrylic or methacrylic acid and its corresponding esters, divalent acrylamides or methacrylamides, N-mers of divalent styrene or methylstyrene (N.gtoreq.2) such as trimers, tetramers;
when Z is2Selected from divalent linking atoms, Z1Is and C2Divalent radicals in which the atoms are directly linkedA linking group; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z1More preferably from divalent C1-20Alkyl, divalent C1-20Aromatic hydrocarbon radical, divalent C1-20Alkoxy, divalent C1-20Aryloxy, divalent C1-20Alkylthio, divalent C1-20Arylthio, most preferably selected from divalent C1-20An alkylthio group; in particular, Z1Preferably from methylene, methylene sulfide, ethylene, propylene, butylene, pentylene, hexylene, divalent phenyl ether, divalent benzyl, divalent ethoxy, divalent butoxy, divalent hexyloxy, most preferably selected from methylene sulfide; when Z is2Selected from said divalent linking groups, Z1Is and C2A divalent linking group in which the atoms are directly linked; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z1More preferably a divalent linking group substituted with an electron-withdrawing divalent linking group, an electron-withdrawing substituent, so that the force-sensitive groupThe more obvious force-induced response effect is obtained; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group1-20Hydrocarbyl/heterohydrocarbyl; by way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, an amide group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, a pyridylidene group;
wherein the content of the first and second substances,
Figure BDA0001936065950000371
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-S-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000372
wherein n is the number of repeating units, can be a fixed value or an average value, and is an integer greater than or equal to 1;
Figure BDA0001936065950000373
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the thio/seleno ester series homolytic mechanism refers to a force sensitive group containing thio/seleno ester force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000374
wherein, W6Each independently selected from a sulfur atom or a selenium atom;
wherein Z is3A divalent linking group containing or not containing a heteroatom, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; by way of example, Z3Selected from, but not limited to, divalent heteroatom linkers, divalent heteroatom group linkers, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein Z is4A divalent linking group containing a heteroatom or not, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; the divalent linking group is selected from but not limited to divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z4More preferably C substituted by cyano, alkyl, aryl, ester, amide, urea, carbamate1-20Hydrocarbyl/heterohydrocarbyl;
wherein the content of the first and second substances,
Figure BDA0001936065950000381
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 1-T-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000382
wherein, W6、Z4、
Figure BDA0001936065950000383
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-T-1;
wherein Z is5Selected from oxygen atom, sulfur atom, selenium atom, silicon atom, carbon atom, nitrogen atom; when Z is5When it is an oxygen atom, a sulfur atom, or a selenium atom, R1 5、R1 6、R1 7Is absent; when Z is5When it is a nitrogen atom, R1 5Exist, R1 6、R1 7Is absent; when Z is5When it is a silicon atom or a carbon atom, R1 5、R1 6Exist, R1 7Is absent;
wherein R is1 5、R1 6、R1 7、R1 8Each independently selected from an atom (including a hydrogen atom), a substituent; r1 5、R1 6、R1 7、R1 8Each independently preferably selected from a hydrogen atom, a halogen atom, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl; r1 5、R1 6、R1 7、R1 8Each independently more preferably from a hydrogen atom, a halogen atom, C1-20Alkyl radical, C1-20Alkenyl radical, C1-20Aryl radical, C1-20Alkoxyacyl group, C1-20Alkoxythioacyl, C1-20Aryloxy acyl group, C1-20Aryloxythioacyl, C1-20Alkylthio acyl radical, C1-20An arylthioacyl group;
wherein Z is6Is a divalent linking group; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring. The divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z6The divalent connecting group is preferably selected from a divalent connecting group with an electron-withdrawing effect and a divalent connecting group substituted by an electron-withdrawing effect substituent, so that the force sensitive group is split evenly and more remarkable force-induced response effect is obtained; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group1-20Hydrocarbyl/heterohydrocarbyl. By way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, an amide group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, and a pyridylidene group.
A typical structure of the formula 1-T-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000384
wherein the content of the first and second substances,
Figure BDA0001936065950000391
independently of one another and participating in force activationPolymer chains or supramolecular polymer chains.
In the present invention, covalent single force sensitive groups based on heterolytic mechanisms include, but are not limited to, the following series: triaryl sulfur salt series, o-phthalaldehyde series, sulfonic acid series, and seleno/seleno-sulfur/seleno-nitrogen series.
In the invention, the covalent single force sensitive group of the triaryl sulfate series heterolysis mechanism refers to a force sensitive group containing triaryl sulfate force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000392
wherein the content of the first and second substances,
Figure BDA0001936065950000393
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, wherein any two of the same ring structure
Figure BDA0001936065950000394
With or without looping.
A typical structure of the formula 2-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000395
wherein the content of the first and second substances,
Figure BDA0001936065950000396
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the ortho-phthalaldehyde series heterolysis mechanism refers to a force sensitive group containing ortho-phthalaldehyde force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:
Figure BDA0001936065950000397
wherein, the ring of M is aliphatic ring, ether ring or the combination of the aliphatic ring, the ether ring and the aromatic ring, the ring-forming atoms of the ring structure are respectively and independently carbon atoms, nitrogen atoms or other hetero atoms, and at least one ring-forming atom is oxygen atom; the hydrogen atoms attached to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein the content of the first and second substances,
Figure BDA0001936065950000398
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 2-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000399
wherein the content of the first and second substances,
Figure BDA00019360659500003910
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the sulfonic acid group series heterolysis mechanism refers to a force-sensitive group containing a sulfonic acid group force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA00019360659500003911
wherein the content of the first and second substances,
Figure BDA00019360659500003912
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 2-C-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500003913
wherein the content of the first and second substances,
Figure BDA00019360659500003914
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the seleno-oxo/seleno-thio/seleno-nitrogen series heterofission mechanism refers to a force-sensitive group containing seleno-oxo/seleno-thio/seleno-nitrogen force-sensitive elements, and the structural general formula includes but is not limited to the following types:
Figure BDA00019360659500003915
wherein each W is independently selected from an oxygen atom, a sulfur atom; wherein the content of the first and second substances,
Figure BDA0001936065950000401
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, to the same atom
Figure BDA0001936065950000402
With or without looping.
Wherein the structures represented by the general formulae 2-D-1 and 2-D-2 are preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000403
wherein W is as defined for formula 2-D-1; wherein the content of the first and second substances,
Figure BDA0001936065950000404
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA0001936065950000405
indicates that n is connected with
Figure BDA0001936065950000406
A nitrogen-containing aromatic ring of (a); the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 5 to 8; except that at least one of the ring-forming atoms is a nitrogen atom and the ring and the selenium atom are connected through the nitrogen atom, the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the value of n is 0, 1 or an integer greater than 1; at different positions
Figure BDA0001936065950000407
Are the same or different; said
Figure BDA0001936065950000408
The structure of (a) is preferably selected from pyridine rings and substituted forms thereof;
Figure BDA0001936065950000409
any two of which are each independently attached to the same atom, including a hydrogen atom, a substituent, and a substituted polymer chain, with or without participation in force activation
Figure BDA00019360659500004010
With or without rings, any two of the same ring structure
Figure BDA00019360659500004011
With or without looping.
Typical structures of the general formulae 2-D-1, 2-D-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500004012
Figure BDA0001936065950000411
wherein X is selected from but not limited to fluorine atom, chlorine atom, bromine atom, cyano group, and isothiocyanato group, preferably from chlorine atom and bromine atom; the definition, selection range and preferable range of W are the same as those of the general formula 2-D-1;
Figure BDA0001936065950000412
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, covalent single force sensitive groups based on the reverse cyclization mechanism include, but are not limited to, the following series: cyclobutane series, monoepoxybutane series, dioxetane series, dinitrocyclobutane series, cyclobutene series, triazole ring series, DA series, hetero DA series, light-controlled DA series, and [4+4] cycloaddition series.
In the invention, the covalent single force-sensitive group of the cyclobutane series reverse cyclization mechanism refers to a force-sensitive group containing a cyclobutane force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following groups:
Figure BDA0001936065950000413
wherein each Q is independently selected from an oxygen atom, a carbon atom; b represents the number of connections to Q, respectively; when each Q is independently selected from oxygen atoms, b ═ 0; when each Q is independently selected from carbon atoms, b ═ 2;
Figure BDA0001936065950000414
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula 3-A-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000415
wherein each J is independently selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof; ar is independently selected from aryl, preferably phenyl; n represents the number of connections to Ar; x0Each independently selected from a halogen atom, preferably from a fluorine atom, a chlorine atom, a bromine atom;
Figure BDA0001936065950000416
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Wherein the structure represented by the general formula 3-A-1-1 is further preferably selected from the following general structures:
Figure BDA0001936065950000417
Figure BDA0001936065950000421
wherein each J' is independently selected from an oxygen atom, a sulfur atom; j is defined, selected and preferred in the same range as in the general formula 3-A-1-3;
Figure BDA0001936065950000422
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
A typical structure of the formula 3-A-1-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000423
Figure BDA0001936065950000431
Figure BDA0001936065950000441
Figure BDA0001936065950000451
Figure BDA0001936065950000461
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j is defined, selected and preferred in the same range as in the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000462
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-A-1-2 is further preferably selected from the following general structures:
Figure BDA0001936065950000463
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000464
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
A typical structure of the formula 3-A-1-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000465
Figure BDA0001936065950000471
Figure BDA0001936065950000481
Figure BDA0001936065950000491
Figure BDA0001936065950000501
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j is defined, selected and preferred in the same range as in the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000502
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-A-1-3 is further preferably selected from the following general structures:
Figure BDA0001936065950000503
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3;
Figure BDA0001936065950000504
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000505
Figure BDA0001936065950000511
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000512
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-A-1-4 is further preferably selected from the following general structures:
Figure BDA0001936065950000513
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3;
Figure BDA0001936065950000514
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000515
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000516
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-A-1-5 is further preferably selected from the following general structures:
Figure BDA0001936065950000517
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3;
Figure BDA0001936065950000518
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-5 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000521
Figure BDA0001936065950000531
wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000532
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-A-1-6 is further preferably selected from the following general structures:
Figure BDA0001936065950000533
Figure BDA0001936065950000541
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000542
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-6 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000543
Figure BDA0001936065950000551
Figure BDA0001936065950000561
wherein, R, R1、R2、R3Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000562
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-A-1-7 is further preferably selected from the following general structures:
Figure BDA0001936065950000563
Figure BDA0001936065950000571
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000572
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000573
Figure BDA0001936065950000581
Figure BDA0001936065950000591
Figure BDA0001936065950000601
wherein, R, R1、R2、R3、R4Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000602
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-A-1-8 is further preferably selected from the following general structures:
Figure BDA0001936065950000603
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000604
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-8 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000605
Figure BDA0001936065950000611
Figure BDA0001936065950000621
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000622
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-A-1-9 is further preferably selected from the following general structures:
Figure BDA0001936065950000623
wherein the definition, the selection range and the preferred range of J are the same as those of the general formula 3-A-1-3; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000624
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-9 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000631
Figure BDA0001936065950000641
Figure BDA0001936065950000651
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000652
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 3-A-1-10 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000653
wherein the content of the first and second substances,
Figure BDA0001936065950000654
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 3-A-1-11 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000655
wherein the content of the first and second substances,
Figure BDA0001936065950000656
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-A-1-12 is further preferably selected from the following general structures:
Figure BDA0001936065950000661
wherein the content of the first and second substances,
Figure BDA0001936065950000662
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-A-1.
Typical structures of the general formula 3-A-1-12 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000663
wherein the content of the first and second substances,
Figure BDA0001936065950000664
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In addition, the typical structure of the covalent single force sensitive group of the cyclobutane series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000665
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000666
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 3-A-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000671
wherein the content of the first and second substances,
Figure BDA0001936065950000672
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 3-A-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000673
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000674
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 3-A-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000675
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation; j' is defined, selected and preferred in the same range as in the general formula 3-A-1-1-6;
Figure BDA0001936065950000676
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent monoradical of the reverse cyclization mechanism of the mono-heterocyclic butane series refers to a radical containing a mono-heterocyclic butane force sensitive element, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0001936065950000677
wherein Q is selected from oxygen atom and carbon atom; b represents the number of connections to Q; when Q is selected from oxygen atom, b ═ 0; when Q is selected from carbon atoms, b ═ 2; d is selected from oxygen atom, sulfur atom and nitrogen atom; a represents the number of connections to D; when D is selected from oxygen atom and sulfur atom, a is 0; when D is selected from a nitrogen atom, a ═ 1;
Figure BDA0001936065950000678
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 3-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000679
Figure BDA0001936065950000681
wherein R is,R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000682
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-B-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000691
wherein the content of the first and second substances,
Figure BDA0001936065950000692
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-B-2.
A typical structure of the formula 3-B-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000693
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000694
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the dioxetane series refers to a force-sensitive group containing a dioxetane force-sensitive element, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0001936065950000695
wherein J is selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom, a secondary amino group and substituted forms thereofFormula (la), methylene and substituted forms thereof; wherein Ar is selected from aromatic rings; the number of ring-forming atoms of the ring is not particularly limited, and a five-membered ring or a six-membered ring is preferable; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; among them, the substituent atom or the substituent is not particularly limited, and it is preferably selected from a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, C1-20Alkyl radical, C1-20Alkylsiloxy group, C1-20Acyloxy, C1-20Alkoxyacyl group, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20An alkylamino group; suitable Ar's may be selected from the following structures by way of example, but the invention is not limited thereto:
Figure BDA0001936065950000701
wherein L is1Is a divalent linking group selected from, but not limited to, oxygen atoms, sulfur atoms, secondary amine groups and substituted forms thereof, methylene groups and substituted forms thereof; l is2Is a divalent linking group selected from, but not limited to, a direct bond, an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, a methylene group and substituted forms thereof, a carbonyl group, a thiocarbonyl group; wherein the content of the first and second substances,
Figure BDA0001936065950000702
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae 3-C-1 to 3-C-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000703
Figure BDA0001936065950000711
Figure BDA0001936065950000721
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000722
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the diazocyclobutane series refers to a force-sensitive group containing a diazocyclobutane force-sensitive element, and the structural general formula of the covalent single force-sensitive group comprises but is not limited to the following groups:
Figure BDA0001936065950000723
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000724
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3-D-1 and 3-D-2 are exemplified below, but the present invention is not limited thereto:
Figure BDA0001936065950000725
Figure BDA0001936065950000731
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000732
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the cyclobutene series reverse cyclization mechanism refers to a force-sensitive group containing cyclobutene force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000733
wherein the content of the first and second substances,
Figure BDA0001936065950000734
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 membered ring, more preferably 6-12 membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above ring structures; n represents the number of linkages to the ring-forming atoms of the cyclic structure; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000735
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3-E-1 to 3-E-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000736
Figure BDA0001936065950000741
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000742
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single-force sensitive groups of the cyclobutane series, the monoheterocyclic butane series, the dioxetane series, the dinitrocyclobutane series and the cyclobutene series reverse cyclization mechanism can also be activated by other actions except mechanical force, for example, the covalent single-force sensitive groups of the cyclobutane series can be subjected to reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force sensitive groups; the dioxetane series covalent single force sensitive group can be subjected to reverse cyclization reaction under one or more of the activation effects of chemistry, biology, heat and the like so as to dissociate the force sensitive group.
In the invention, the covalent single force-sensitive group of the triazole ring series reverse cyclization mechanism refers to a force-sensitive group containing a triazole ring force-sensitive element, and the structural general formula of the covalent single force-sensitive group comprises but is not limited to the following groups:
Figure BDA0001936065950000751
wherein the content of the first and second substances,
Figure BDA0001936065950000752
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation. Wherein the structure represented by the general formula 3-F-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000753
wherein the content of the first and second substances,
Figure BDA0001936065950000754
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-F-1.
A typical structure of the formula 3-F-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000755
wherein the content of the first and second substances,
Figure BDA0001936065950000756
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the DA series reverse cyclization mechanism refers to a force-sensitive group containing DA force-sensitive elements, and the structural general formula of the covalent single force-sensitive group comprises but is not limited to the following classes:
Figure BDA0001936065950000757
wherein, each I is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;
Figure BDA0001936065950000758
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;
Figure BDA0001936065950000759
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by formula 3-G-1 is preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500007510
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA00019360659500007511
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-1.
A typical structure of the formula 3-G-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500007512
Figure BDA0001936065950000761
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000762
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 3-G-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000763
wherein each R is independently selected from any suitable atom (including hydrogen)Atoms), substituents, and substituted polymer chains that do not participate in force activation;
Figure BDA0001936065950000764
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-3 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000765
Figure BDA0001936065950000771
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000772
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-3.
Typical structures of the general formula 3-G-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000773
Figure BDA0001936065950000781
Figure BDA0001936065950000791
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000792
are independent and participate inThe force activated substituted polymer chains or supramolecular polymer chains are linked.
Wherein the structure represented by formula 3-G-4 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000793
wherein the content of the first and second substances,
Figure BDA0001936065950000794
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-4.
Typical structures of the general formula 3-G-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000795
Figure BDA0001936065950000801
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000802
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-5 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000803
wherein the content of the first and second substances,
Figure BDA0001936065950000804
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-5.
Wherein the structure represented by the general formula 3-G-5-1 is further preferably selected from the following general structures:
Figure BDA0001936065950000805
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000806
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-5.
A typical structure of the formula 3-G-5-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000807
Figure BDA0001936065950000811
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000812
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-G-5-2 is further preferably selected from the following general structures:
Figure BDA0001936065950000813
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000814
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-5.
A typical structure of the formula 3-G-5-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000815
Figure BDA0001936065950000821
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000822
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-5-3 is further preferably selected from the following general structures:
Figure BDA0001936065950000823
wherein R is1Each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000824
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-5.
Typical structures of the general formula 3-G-5-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000825
Figure BDA0001936065950000831
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000832
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-6 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000833
wherein the content of the first and second substances,
Figure BDA0001936065950000834
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-6.
Typical structures of the general formula 3-G-6 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000835
wherein, R, R1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000836
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-7 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000841
wherein the content of the first and second substances,
Figure BDA0001936065950000842
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-7.
Wherein the structure represented by the general formula 3-G-7-1 is further preferably selected from the following general structures:
Figure BDA0001936065950000843
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000844
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-7.
A typical structure of the formula 3-G-7-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000845
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000846
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-G-7-2 is further preferably selected from the following general structures:
Figure BDA0001936065950000847
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000848
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-7.
A typical structure of the formula 3-G-7-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000849
Figure BDA0001936065950000851
wherein, R, R1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000852
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-G-8 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000853
wherein the content of the first and second substances,
Figure BDA0001936065950000854
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-G-8.
Typical structures of the general formula 3-G-8 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000855
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000861
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
The typical structure of the covalent single force sensitive group of the DA series reverse cyclization mechanism can also be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950000862
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000863
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the hetero DA series reverse cyclization mechanism refers to a force-sensitive group containing a hetero DA force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950000864
wherein, P1Selected from oxygen atom, sulfur atom, nitrogen atom; p2Selected from carbon atoms, nitrogen atoms; c. C1、c2Respectively represent and P1、P2The number of connected connections; when P is present1When selected from oxygen atom, sulfur atom, c10; when P is present1、P2When selected from nitrogen atoms, c1、c21 is ═ 1; when P is present2When selected from carbon atoms, c22; i is selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;
Figure BDA0001936065950000865
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may have a positive signA charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;
Figure BDA0001936065950000866
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula 3-H-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000867
wherein the content of the first and second substances,
Figure BDA0001936065950000868
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-1.
A typical structure of the formula 3-H-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000869
Figure BDA0001936065950000871
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000872
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-H-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000873
wherein the content of the first and second substances,
Figure BDA0001936065950000874
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-2.
A typical structure of the formula 3-H-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000875
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000876
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-H-3 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000877
wherein the content of the first and second substances,
Figure BDA0001936065950000878
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-3.
A typical structure of the formula 3-H-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000881
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950000882
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-H-4 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000883
wherein the content of the first and second substances,
Figure BDA0001936065950000884
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-4.
Typical structures of the general formula 3-H-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000885
Figure BDA0001936065950000891
Figure BDA0001936065950000901
wherein, R, R1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000902
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-H-5 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000903
wherein the content of the first and second substances,
Figure BDA0001936065950000904
the definition, selection range and preferred range of (A) are the same as those of the general formula 3-H-5。
Typical structures of the general formula 3-H-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000911
Figure BDA0001936065950000921
wherein, R, R1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000922
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 3-H-6 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000923
wherein the content of the first and second substances,
Figure BDA0001936065950000924
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-H-6.
Typical structures of the general formula 3-H-6 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000925
Figure BDA0001936065950000931
wherein, R, R1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000932
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
The typical structure of the covalent single force sensitive group of the heteroDA series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000933
wherein, R, R1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950000934
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the light-controlled DA series reverse cyclization mechanism refers to a force-sensitive group which contains a light-controlled locking element and a DA element sensitive to mechanical force, wherein the DA element can be used as a part of the light-controlled locking element; the existence of the light-operated locking element enables the force-sensitive clusters to have different structures under different illumination conditions and show different response effects on mechanical force, thereby achieving the purpose of locking/unlocking the force-sensitive elements; under the condition of light-operated unlocking, the DA force-sensitive element can perform inverse DA chemical reaction under the action of mechanical force, so that the polymer directly and/or indirectly generates chemical signal change, specific response to mechanical force is achieved, and force-induced response performance/effect is obtained; when the force-sensitive element is locked, it cannot be activated by mechanical force to express the force-sensitive property, or is more difficult to be activated by mechanical force to express the force-sensitive property. By utilizing the characteristics, the mechanochemical performance of the material can be regulated and controlled by selecting specific illumination conditions, the locking/unlocking regulation effect is achieved, and the applicability and the functional responsiveness of the force sensitive group are improved. Wherein, ultraviolet light (generally, ultraviolet light with a wavelength range of 310-380 nm) is selected to lock the force sensitive groups, and visible light (generally, visible light with a wavelength range of more than 420 nm) is selected to unlock the force sensitive groups. The ultraviolet light and the visible light used as the light source in the present invention have various and unlimited sources, and may be ultraviolet light or visible light directly generated by a high pressure mercury lamp, a metal halogen lamp, a mercury lamp, a xenon lamp, an LED lamp, etc. with a desired wavelength, or ultraviolet light or visible light obtained by energy transfer (including up-conversion fluorescence or down-conversion fluorescence) of a fluorophore; the fluorophore may be selected from organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, organic-inorganic hybrid fluorophores, and the like.
In the invention, the light control locking element comprises the following structural units:
Figure BDA0001936065950000941
wherein the content of the first and second substances,
Figure BDA0001936065950000942
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of which
Figure BDA0001936065950000943
With or without rings including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
In the invention, the Diels-Alder force-sensitive element contains at least one of the following structural units:
Figure BDA0001936065950000944
wherein, K0Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, a0Represents a group K0The number of connected connections; when K is0When selected from oxygen atom, sulfur atom, a00; when K is0When selected from nitrogen atoms, a01 is ═ 1; when K is0When selected from carbon atoms, a0＝2；
Figure BDA0001936065950000945
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In the invention, the covalent single force sensitive group of the reverse cyclization mechanism of the light-operated DA series has a structural general formula including but not limited to the following classes:
Figure BDA0001936065950000946
wherein, K1、K2、K3、K4、K5、K6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K1、K2Or K3、 K4Or K5、K6At least one of them is selected from carbon atoms; a is1、a2、a3、a4、a5、a6Respectively represent and K1、K2、K3、K4、K5、K6The number of connected connections; when K is1、K2、K3、K4、K5、K6Each independently selected from an oxygen atom and a sulfur atom1、a2、a3、a4、a5、a60; when K is1、K2、K3、K4、K5、K6Each independently selected from nitrogen atoms, a1、a2、a3、a4、a5、a61 is ═ 1; when K is1、K2、K3、K4、 K5、K6Each independently selected from carbon atoms, a1、a2、a3、a4、a5、a6＝2；I1、I2、I3Each independently absent, or each independently selected from an oxygen atom, 1,1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof; when I is1、I2、I3Each independently absent, b ═ 2; when I is1、I2、I3Each independently selected from the group consisting of an oxygen atom, 1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof, b ═ 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (
Figure BDA0001936065950000947
n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c1、C2、C3、C4、C5、C6Represent carbon atoms in different positions;
Figure BDA0001936065950000948
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and preferably at K1And K2K to3And K4K to5And K6C to1And C2C to3And C4C to5And C6Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not; wherein, K1And K2K to3And K4K to5And K6The ring formed between preferably has the following structure:
Figure BDA0001936065950000951
C1and C2C to3And C4The ring formed between preferably has the following structure:
Figure BDA0001936065950000952
C5and C6The ring formed between preferably has the following structure:
Figure BDA0001936065950000953
wherein the structure represented by the general formula 3-I-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000954
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R1、R2No ring is formed between the two;
Figure BDA0001936065950000955
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; e1、E2Each independently selected from any one of the following structures:
Figure BDA0001936065950000956
a typical structure of the formula 3-I-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000961
Figure BDA0001936065950000971
wherein the structure represented by the general formula 3-I-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000981
wherein E is1、E2The definition, selection range and preferable range of the formula (I) are the same as those of the general formula 3-I-1-1;
Figure BDA0001936065950000982
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the general formula 3-I-2 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000983
wherein the structure represented by the general formula 3-I-3 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950000984
Figure BDA0001936065950000991
wherein R is1、R2、R3、R4Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two; e is selected from any one of the following structures:
Figure BDA0001936065950000992
wherein the content of the first and second substances,
Figure BDA0001936065950000993
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formula 3-I-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950000994
Figure BDA0001936065950001001
wherein the structure represented by the general formula 3-I-4 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001002
Figure BDA0001936065950001011
wherein the definition, the selection range and the preferred range of E are the same as those of the general formula 3-I-3-1;
Figure BDA0001936065950001012
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001013
wherein the structure represented by the general formula 3-I-5 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001014
Figure BDA0001936065950001021
wherein R is1、R2、R3、R4、R5、R6Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two;
Figure BDA0001936065950001022
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001023
Figure BDA0001936065950001031
wherein the structure represented by the general formula 3-I-6 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001032
wherein the content of the first and second substances,
Figure BDA0001936065950001033
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-6 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001034
wherein the structure represented by the general formula 3-I-7 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001035
Figure BDA0001936065950001041
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R1、R2No ring is formed between the two; the definition, the selection range and the preferred range of the E are the same as those of the general formula 3-I-3-1; f is selected from any one of the following structures:
Figure BDA0001936065950001042
Figure BDA0001936065950001043
Figure BDA0001936065950001044
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001045
Figure BDA0001936065950001051
Figure BDA0001936065950001061
Figure BDA0001936065950001071
wherein the structure represented by the general formula 3-I-8 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001072
wherein the definition, the selection range and the preferred range of E are the same as those of the general formula 3-I-3-1; the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;
Figure BDA0001936065950001073
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-8 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001074
Figure BDA0001936065950001081
wherein the structure represented by the general formula 3-I-9 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001082
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain with or without participation in force activation, and R1、R2No ring is formed between the two; g is selected from any one of the following structures:
Figure BDA0001936065950001083
Figure BDA0001936065950001084
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-9 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001085
Figure BDA0001936065950001091
Figure BDA0001936065950001101
wherein the structure represented by the general formula 3-I-10 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001102
wherein, the definition, the selection range and the preferred range of G are the same as those of the general formula 3-I-9-1;
Figure BDA0001936065950001103
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-10 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001104
Figure BDA0001936065950001111
wherein the structure represented by the general formula 3-I-11 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001112
wherein R is1、R2、R3、R4Each independently selected from any suitable atom (including hydrogen atoms), alkyl, aryl, heteroaryl, and the likeA substituent and a substituted polymer chain which is or is not involved in force activation, and no ring is formed between every two of the substituent and the substituted polymer chain; the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;
Figure BDA0001936065950001113
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-11 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001114
Figure BDA0001936065950001121
wherein the structure represented by the general formula 3-I-12 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001131
wherein, the definition, the selection range and the preferred range of F are the same as those of the general formula 3-I-7-1;
Figure BDA0001936065950001132
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 3 to I-12 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001133
wherein, R in the typical structure example of the 3-I series is independently selected from any suitable atom (including hydrogen atom), substituent and substituted polymer chain not participating in force activation, preferably from hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl, amino, carboxyl, ester group, carboxyl,Cyano, methyl, ethyl, propyl, vinyl, trifluoromethyl, phenyl, pyridyl, more preferably selected from hydrogen atom, fluorine atom, cyano, methyl, phenyl; r1、R2Each independently selected from any suitable hydrogen atom, substituted alkyl group, and substituted polymer chain not involved in force activation; r0Each independently selected from the group consisting of: -H, -CH3、-F、-Cl、-Br、-COOH、-CN、
Figure BDA0001936065950001134
Figure BDA0001936065950001135
Figure BDA0001936065950001136
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of DA series, hybrid DA series and light-operated DA series reverse cyclization mechanism can also carry out reverse cyclization reaction through thermal activation so as to dissociate the force sensitive group.
In the present invention, the covalent single force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism refers to a force-sensitive group containing a [4+4] cycloaddition force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0001936065950001137
Figure BDA0001936065950001141
wherein the content of the first and second substances,
Figure BDA0001936065950001142
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted, orOr unsubstituted, wherein, when the ring-forming atom is selected from nitrogen atoms, the nitrogen atom may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, an aza-benzene, an aza-naphthalene, an aza-anthracene or a substituted form of the above groups; i is6～I14Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;
Figure BDA0001936065950001143
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula 3-J-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001144
wherein R is1、R2、R3、R4Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, and which does not form a ring between each two;
Figure BDA0001936065950001145
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-1.
A typical structure of the formula 3-J-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001146
wherein the content of the first and second substances,
Figure BDA0001936065950001147
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001148
Figure BDA0001936065950001151
wherein the content of the first and second substances,
Figure BDA0001936065950001152
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-2.
A typical structure of the formula 3-J-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001153
wherein the content of the first and second substances,
Figure BDA0001936065950001154
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-3 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001155
wherein the content of the first and second substances,
Figure BDA0001936065950001156
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-3.
Typical structures of the general formula 3-J-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001161
wherein the content of the first and second substances,
Figure BDA0001936065950001162
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the force sensitive groups of formula 3-J-4, which are preferably selected from a subset of the following general structures:
Figure BDA0001936065950001163
wherein the content of the first and second substances,
Figure BDA0001936065950001164
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-4.
Typical structures of the general formula 3-J-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001165
wherein the content of the first and second substances,
Figure BDA0001936065950001166
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the force sensitive groups of formula 3-J-5, which are preferably selected from a subset of the following general structures:
Figure BDA0001936065950001167
wherein the content of the first and second substances,
Figure BDA0001936065950001168
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-5.
Typical structures of the general formula 3-J-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001169
wherein the content of the first and second substances,
Figure BDA00019360659500011610
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the force sensitive groups of formula 3-J-6, which are preferably selected from a subset of the following general structures:
Figure BDA00019360659500011611
wherein the content of the first and second substances,
Figure BDA00019360659500011612
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-6.
Typical structures of the general formulae 3-J-6 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001171
wherein R is1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001172
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-7 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001173
wherein the content of the first and second substances,
Figure BDA0001936065950001174
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-7.
Typical structures of the general formula 3-J-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001175
wherein the content of the first and second substances,
Figure BDA0001936065950001176
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-8 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001177
wherein the content of the first and second substances,
Figure BDA0001936065950001178
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-8.
Typical structures of the general formula 3-J-8 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001179
wherein the content of the first and second substances,
Figure BDA00019360659500011710
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-9 is preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500011711
wherein the content of the first and second substances,
Figure BDA00019360659500011712
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-9.
Typical structures of the general formula 3-J-9 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001181
wherein the content of the first and second substances,
Figure BDA0001936065950001182
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-10 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001183
wherein the content of the first and second substances,
Figure BDA0001936065950001184
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-10.
Typical structures of the general formula 3-J-10 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001185
wherein the content of the first and second substances,
Figure BDA0001936065950001186
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-11 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001187
wherein the content of the first and second substances,
Figure BDA0001936065950001188
definition of (1)The selection range and the preferred range are the same as those of the general formula 3-J-11.
Typical structures of the general formula 3-J-11 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001189
Figure BDA0001936065950001191
wherein R is1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001192
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the force sensitive groups of formula 3-J-12, which are preferably selected from a subset of the following general structures:
Figure BDA0001936065950001193
wherein the content of the first and second substances,
Figure BDA0001936065950001194
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-12.
Typical structures of the general formula 3-J-12 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001195
wherein the content of the first and second substances,
Figure BDA0001936065950001196
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-13 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001197
wherein the content of the first and second substances,
Figure BDA0001936065950001198
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-13.
Typical structures of the general formula 3-J-13 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001199
Figure BDA0001936065950001201
wherein R is1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001202
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-14 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001203
wherein the content of the first and second substances,
Figure BDA0001936065950001204
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-14.
Typical structures of the general formula 3-J-14 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001205
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001206
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-15 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001211
wherein the content of the first and second substances,
Figure BDA0001936065950001212
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-15.
Typical structures of the general formula 3-J-15 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001213
wherein R is1、R2Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001214
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-16 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001215
wherein the content of the first and second substances,
Figure BDA0001936065950001216
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-16.
Typical structures of the general formulae 3-J-16 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001217
Figure BDA0001936065950001221
wherein R is1Each independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain not involved in force activation;
Figure BDA0001936065950001222
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 3-J-17 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001223
Figure BDA0001936065950001231
wherein the content of the first and second substances,
Figure BDA0001936065950001232
the definition, selection range and preferable range of (A) are the same as those of the general formula 3-J-17.
Typical structures of the general formula 3-J-17 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001233
Figure BDA0001936065950001241
wherein the content of the first and second substances,
Figure BDA0001936065950001242
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
The typical structure of the covalent single force sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001243
Figure BDA0001936065950001251
wherein the content of the first and second substances,
Figure BDA0001936065950001252
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also carry out reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force-sensitive group.
In the present invention, covalent single force sensitive groups based on the electrocyclization mechanism include, but are not limited to, the following series: six-membered ring series, five-membered ring series, three-membered ring series.
In the present invention, the covalent single force sensitive group of the six-membered ring series electrical cyclization mechanism refers to a single force sensitive group containing six-membered ring force sensitive elements, and the structural general formula includes but is not limited to the following groups:
Figure BDA0001936065950001253
wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R and nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;
Figure BDA0001936065950001254
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain, whether or not participating in force activation, different on the same atom
Figure BDA0001936065950001255
Can be linked to form a ring, on different atoms
Figure BDA0001936065950001256
Or can be connected into a ring. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
The six-membered ring monomer containing the general structural formula (4-A-1) of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001257
Figure BDA0001936065950001261
wherein, X1Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from an oxygen atom; y is1Each independently selected from C-R, nitrogen atom; z1Is selected from C- (R)2Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)2A nitrogen atom; z2Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)2Nitrogen atom, preferably C- (R)2A nitrogen atom; when Z is1Or Z2Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)2When connected to it
Figure BDA0001936065950001262
The number is 0;
Figure BDA0001936065950001263
representing an arbitrary number of elementsAn aromatic ring of (2); n is a total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the ring-constituting atoms, and is 0, 1 or an integer X, Y, R greater than 1,
Figure BDA0001936065950001264
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001265
Figure BDA0001936065950001271
Figure BDA0001936065950001281
wherein, X, X1、Y、Y1、R、Z1、Z2、
Figure BDA0001936065950001282
n、
Figure BDA0001936065950001283
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001284
Figure BDA0001936065950001291
wherein, X2Each independently selected from carbon atom, oxygen atomA sulfur atom, N-R; x3Each independently selected from the group consisting of an oxygen atom, a sulfur atom, N-R; x, X1、Y、Y1、R、Z1、Z2、
Figure BDA0001936065950001292
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-1) is exemplified by the following structures:
Figure BDA0001936065950001293
Figure BDA0001936065950001301
Figure BDA0001936065950001311
Figure BDA0001936065950001321
Figure BDA0001936065950001331
Figure BDA0001936065950001341
Figure BDA0001936065950001351
Figure BDA0001936065950001361
wherein, X, X1、X2、X3、Y、Y1The selection range of R is as described in the series of force-sensitive groups, and is not described in detail herein;
Figure BDA0001936065950001362
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-2) of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001363
wherein, X, R, Z1、Z2、
Figure BDA0001936065950001371
n、
Figure BDA0001936065950001372
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-2) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001373
wherein, X, Z1、Z2、
Figure BDA0001936065950001374
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted;
Figure BDA0001936065950001375
represents an aromatic ring having an arbitrary number of elements.
The six-membered ring monomer having the general structural formula (4-A-2) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001376
wherein, X, R, Z1、Z2、
Figure BDA0001936065950001377
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-2) is exemplified by the following structures:
Figure BDA0001936065950001378
Figure BDA0001936065950001379
wherein the content of the first and second substances,
Figure BDA00019360659500013710
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA00019360659500013711
wherein X, M,
Figure BDA00019360659500013712
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted.
The six-membered ring monomer having the general structural formula (4-A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001381
wherein X, M, n,
Figure BDA0001936065950001382
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted;
Figure BDA0001936065950001383
represents an aromatic ring having an arbitrary number of elements.
The six-membered ring monomer having the general structural formula (4-A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001384
wherein M, R,
Figure BDA0001936065950001385
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-3) is exemplified by the following structures:
Figure BDA0001936065950001386
wherein the content of the first and second substances,
Figure BDA0001936065950001387
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001388
wherein, X, Y, Z1、Z2、
Figure BDA0001936065950001389
The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
The six-membered ring monomer having the general structural formula (4-A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA00019360659500013810
Figure BDA0001936065950001391
wherein, X, Y, Z1、Z2、
Figure BDA0001936065950001392
n、
Figure BDA0001936065950001393
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001394
wherein, X, Y, R, Z1、Z2、
Figure BDA0001936065950001395
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-4) is exemplified by the following structures:
Figure BDA0001936065950001396
wherein, the selection range of X, Y is as described in the series of force-sensitive groups, and is not described in detail herein;
Figure BDA0001936065950001397
are independent of each other and participate in forceThe activated polymer chains or supramolecular polymer chains are linked.
The six-membered ring monomer containing the general structural formula (4-A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001398
wherein the content of the first and second substances,
Figure BDA0001936065950001399
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA00019360659500013910
wherein the content of the first and second substances,
Figure BDA00019360659500013911
n、
Figure BDA00019360659500013912
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA00019360659500013913
wherein R is,
Figure BDA00019360659500013914
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-5) is exemplified by the following structures:
Figure BDA0001936065950001401
wherein the content of the first and second substances,
Figure BDA0001936065950001402
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001403
wherein X, R,
Figure BDA0001936065950001404
n、
Figure BDA0001936065950001405
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001406
wherein X, R,
Figure BDA0001936065950001407
n、
Figure BDA0001936065950001408
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001411
wherein R is,
Figure BDA0001936065950001412
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-6) is exemplified by the following structures:
Figure BDA0001936065950001413
Figure BDA0001936065950001421
Figure BDA0001936065950001431
wherein, the selection range of X is as the previous description of the series of force-sensitive groups, and the description is omitted;
Figure BDA0001936065950001432
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001433
wherein, X, Z2、
Figure BDA0001936065950001434
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001435
wherein, X, Z2、
Figure BDA0001936065950001436
The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
The six-membered ring monomer having the general structural formula (4-A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001437
wherein R is,
Figure BDA0001936065950001438
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-7) is exemplified by the following structures:
Figure BDA0001936065950001439
Figure BDA0001936065950001441
Figure BDA0001936065950001451
Figure BDA0001936065950001461
wherein the content of the first and second substances,
Figure BDA0001936065950001462
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the five-membered ring series electrical cyclization mechanism is a force sensitive group containing five-membered ring force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:
Figure BDA0001936065950001463
wherein A is0Is selected from
Figure BDA0001936065950001464
A1Is selected from
Figure BDA0001936065950001465
A2Is selected from
Figure BDA0001936065950001466
Figure BDA0001936065950001467
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula 4-B-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001468
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950001469
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
wherein, T1Each independently is a substituent group, preferablySelected as electron withdrawing groups, and two T1Can be connected to form a ring; by way of example, such electron-withdrawing groups include, but are not limited to, acyl groups, aldehyde groups, amide groups, sulfonic acid groups, nitrile groups, quaternary amine groups, ester groups, halogenated alkyl groups, and the like; wherein, T1Each independently is preferably acyl, ester group, nitrile group, fluoroalkyl group; specifically, T is exemplified1Exemplary structures of (a) include, but are not limited to, the following:
Figure BDA00019360659500014610
wherein the content of the first and second substances,
Figure BDA00019360659500014611
is a conjugated ring structure or a heterocyclic ring structure containing double bonds; position 1 is attached to a force-activatable bond and position 2 is attached to another linking atom of the five-membered ring; n is
Figure BDA00019360659500014612
Is 0, 1 or an integer greater than 1, m is the number of R therein, which is 0, 1 or an integer greater than 1; wherein, the ring-forming atom at the 1-position side and
Figure BDA00019360659500014613
the ring-forming atoms on the side of the position 2 and the ring-forming atoms on the symmetry axis shown by the dotted line are connected with R; the ring structure is preferably
Figure BDA00019360659500014614
Because it is sensitive to light at the same time, it can realize double response of force and light.
A typical structure of the formula 4-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500014615
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, andsubstituted polymer chains that do not participate in force activation;
Figure BDA0001936065950001471
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
specifically, the typical structure of the formula 4-B-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001472
wherein the content of the first and second substances,
Figure BDA0001936065950001473
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure of formula 4-B-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001474
wherein A is0、
Figure BDA0001936065950001475
The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2;
wherein the content of the first and second substances,
Figure BDA0001936065950001476
is a conjugated ring structure or a heterocyclic structure with positive charge; n is
Figure BDA0001936065950001477
The total number of (a) is 0, 1 or an integer greater than 1; the ring structure is preferably
Figure BDA0001936065950001478
Wherein the content of the first and second substances,
Figure BDA0001936065950001479
is an aromatic ring structure; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; wherein the content of the first and second substances,
Figure BDA00019360659500014710
to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; n is
Figure BDA00019360659500014711
The total number of (a) is 0, 1 or an integer greater than 1; by way of example only, the following may be mentioned,
Figure BDA00019360659500014712
exemplary structures of (a) include, but are not limited to, the following:
Figure BDA00019360659500014713
among them, the force sensitive group of the general formula 4-B-2 is further preferably selected from the following general structure:
Figure BDA00019360659500014714
wherein A is0、
Figure BDA00019360659500014715
The definition and the selection range of the formula (I) are the same as those of the general formula 4-B-2;
Figure BDA00019360659500014716
the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-1;
Figure BDA00019360659500014717
the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-2;
wherein the content of the first and second substances,
Figure BDA00019360659500014718
is a conjugated ring structure or a heterocyclic ring structure with strong electron-withdrawing groups and/or heteroatoms, n is
Figure BDA00019360659500014719
The total number of (a) is 0, 1 or an integer greater than 1; the strong electron-withdrawing group is preferably nitro; the heteroatom is preferably a nitrogen atom; by way of example only, the following may be mentioned,
Figure BDA00019360659500014720
exemplary structures of (a) include, but are not limited to, the following:
Figure BDA0001936065950001481
wherein the content of the first and second substances,
Figure BDA0001936065950001482
the definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-2-2; wherein the content of the first and second substances,
Figure BDA0001936065950001483
is a conjugated ring structure or a conjugated heterocyclic structure, n is
Figure BDA0001936065950001484
The total number of (a) is 0, 1 or an integer greater than 1; the ring structure is preferably
Figure BDA0001936065950001485
A typical structure of the formula 4-B-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001486
wherein the content of the first and second substances,
Figure BDA0001936065950001487
each independently of any suitable atom (including hydrogen atom)A), substituents, and substituted polymer chains that may or may not participate in force activation;
specifically, the typical structure of the formula 4-B-2 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001488
wherein the content of the first and second substances,
Figure BDA0001936065950001489
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structures represented by the general formulae 4-B-3 to 4-B-6 are preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500014810
wherein A is1The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA00019360659500014811
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
wherein, T2Each independently a substituent group, preferably an electron-withdrawing group, and two T's in the general formulae 4-B-4-1, 4-B-6-12Can be connected to form a ring; by way of example, such electron-withdrawing groups include, but are not limited to, acyl groups, aldehyde groups, amide groups, sulfonic acid groups, nitrile groups, quaternary amine groups, ester groups, halogenated alkyl groups, and the like; wherein, T2Each independently is preferably acyl, ester group, nitrile group, fluoroalkyl group; specifically, T is not connected to form a ring, for example2Exemplary structures of (a) include, but are not limited to, the following: :
Figure BDA0001936065950001491
specifically, as an example, two T's in the general formulae 4-B-4-1 and 4-B-6-1, which are linked to form a ring2Selected from, but not limited to:
Figure BDA0001936065950001492
wherein the content of the first and second substances,
Figure BDA0001936065950001493
is a heterocyclic ring containing at least one nitrogen atom, AxIs a carbon atom or a nitrogen atom, and n is a ring member attached to a heterocyclic ring
Figure BDA0001936065950001494
The total number of (a) is 1 or an integer greater than 1; the heterocyclic ring containing at least one nitrogen atom is preferably an aromatic heterocyclic ring containing at least one nitrogen atom;
when A isxIn the case of carbon atoms, suitable heterocyclic structures containing at least one nitrogen atom include, by way of example and not limitation, the following:
Figure BDA0001936065950001495
when A isxIn the case of a nitrogen atom, suitable heterocyclic structures containing at least two nitrogen atoms include, by way of example and not limitation, the following:
Figure BDA0001936065950001496
wherein the content of the first and second substances,
Figure BDA0001936065950001497
is an aromatic ring structure, each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation; n is the total number of R numbers, and is 0, 1 or an integer more than 1; by way of example, the
Figure BDA0001936065950001498
Exemplary structures of (a) include, but are not limited to, the following:
Figure BDA0001936065950001499
among them, the structure represented by the general formulae 4-B-3 to 4-B-6 is more preferably:
Figure BDA00019360659500014910
wherein E is1Each independently selected from one of two structures shown below:
Figure BDA00019360659500014911
wherein the content of the first and second substances,
Figure BDA00019360659500014912
each independently is an aromatic ring structure, n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1;
by way of example, E1In (1),
Figure BDA0001936065950001501
exemplary structures of (a) include, but are not limited to, the following:
Figure BDA0001936065950001502
by way of example, E1In (1),
Figure BDA0001936065950001503
including but not limited to the following:
Figure BDA0001936065950001504
wherein E is2Are any suitable atoms (including hydrogen atoms), substituents, and substituted polymer chains, with or without participation in force activation, preferably E1(ii) a In the same structure, when E2Is selected in the range of E1When E is greater1And E2Are independent of each other;
wherein the definition, the selection range and the preferable range of the other parameters are shown as the general formula 4-B-3-1 to 4-B-6-1.
Among them, the general formulae 4-B-3 to 4-B-6 are more preferably spiro structures represented by the following formulae:
Figure BDA0001936065950001505
wherein, the linking group ExEach independently selected from a direct bond,
Figure BDA0001936065950001506
Wherein the group consisting of a linking group ExThe ring structure to which it is attached being substituted E1The ring structures contained in (1) may be the same or different; the definition, selection range and preferable range of the other parameters are shown as general formulas 4-B-3-1 to 4-B-6-1.
In one embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably that the force-sensitive element is connected with some specific structures so as to realize a structure responding to specific metal ions, so that the force-sensitive group has ion detection function besides force response. By way of example, typical structures that can achieve a response to a particular metal ion are listed below, but the invention is not limited thereto:
Cu2+：
Figure BDA0001936065950001507
Hg2+：
Figure BDA0001936065950001508
Fe3+：
Figure BDA0001936065950001511
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001512
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In another embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably a structure capable of chelating with metal ions and achieving forced ion release, and typical structures capable of chelating with metal ions and achieving forced ion release are listed as follows by way of example, but the present invention is not limited thereto:
Figure BDA0001936065950001513
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation,
Figure BDA0001936065950001514
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In another embodiment of the present invention, the general formula 4-B-3-1-1-1 is preferably a structure which is linked to an energy receptor and can effect energy transfer upon force activation; by way of example, typical structures that can be attached to an energy receptor and that can effect energy transfer upon force activation are as follows, but the invention is not limited thereto:
Figure BDA0001936065950001515
wherein L is any suitable covalent linking group having a length of less than 10 nm; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001516
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Other typical structures shown in the general formula 4-B-3 are exemplified below, but the present invention is not limited thereto:
Figure BDA0001936065950001521
wherein A is1The definition and selection range of (A) are the same as those of the general formula 4-B-3, preferably
Figure BDA0001936065950001522
Wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001523
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure shown by the general formula 4-B-3 is further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001524
Figure BDA0001936065950001531
Figure BDA0001936065950001541
Figure BDA0001936065950001551
Figure BDA0001936065950001561
Figure BDA0001936065950001571
wherein A is1The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3;
Figure BDA0001936065950001572
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
The typical structure shown in the formula 4-B-4 is exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001573
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950001574
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure shown by the general formula 4-B-4 is further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001575
Figure BDA0001936065950001581
Figure BDA0001936065950001591
wherein the content of the first and second substances,
Figure BDA0001936065950001592
are independent and participate inThe force activated substituted polymer chains or supramolecular polymer chains are linked.
The typical structure shown in the formula 4-B-5 is exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001593
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950001594
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure shown by the general formula 4-B-5 is further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001595
Figure BDA0001936065950001601
wherein the content of the first and second substances,
Figure BDA0001936065950001602
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures shown by the general formula 4-B-6 are exemplified below, but the present invention is not limited thereto:
Figure BDA0001936065950001603
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950001604
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure shown by the general formula 4-B-6 is further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001605
Figure BDA0001936065950001611
wherein the content of the first and second substances,
Figure BDA0001936065950001612
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 4-B-7 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001613
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0001936065950001614
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein E is1、E2The definition, selection range and preferable range of the formula (I) are the same as those of the general formula 4-B-3-1-1;
wherein the content of the first and second substances,
Figure BDA0001936065950001615
is an aromatic ring structure, is a linking position, wherein position 1 is linked to a carbon atom and position 2 is linked to an oxygen atom; wherein the ring-forming atom at the 1-position side and the ring-forming atom on the symmetry axis shown by the dotted line are bonded to R, and the ring-forming atom at the 2-position sideRing-forming atoms and
Figure BDA0001936065950001616
connecting; n is the total number of R's bonded to the atoms constituting the aromatic ring, and m is
Figure BDA0001936065950001621
The total number of the number; by way of example, such ring structures include, but are not limited to, the following:
Figure BDA0001936065950001622
wherein, T3Each independently selected from one of two structures shown below:
Figure BDA0001936065950001623
two T in the same type3When selected from the same structure, T3The specific structures of the components can be the same or different; wherein the content of the first and second substances,
Figure BDA0001936065950001624
each independently is an aromatic ring structure, n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1;
by way of example, T3In (1),
Figure BDA0001936065950001625
exemplary structures of (a) include, but are not limited to, the following:
Figure BDA0001936065950001626
by way of example, T3In (1),
Figure BDA0001936065950001627
exemplary structures of (a) include, but are not limited to, the following:
Figure BDA0001936065950001628
typical structures of the general formula 4-B-7 are exemplified below, but the present invention is not limited thereto:
Figure BDA0001936065950001629
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA00019360659500016210
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure of the formula 4-B-7 is further exemplified below, but the present invention is not limited thereto:
Figure BDA0001936065950001631
wherein the content of the first and second substances,
Figure BDA0001936065950001632
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the electrical cyclization mechanism of the three-membered ring series refers to a force-sensitive group containing three-membered ring (including three-membered ring and four-membered/five-membered ring) force-sensitive elements, and the structural general formula includes but is not limited to the following groups:
Figure BDA0001936065950001633
wherein the content of the first and second substances,
Figure BDA0001936065950001634
each independently of any suitable atom (including hydrogen atom)A), substituents, and substituted polymer chains that may or may not participate in force activation; a is selected from-O-, -S-),
Figure BDA0001936065950001635
Wherein, each E is independently selected from hydrogen atom, halogen atom, alkyl and alkoxy.
Wherein the structure represented by the general formula 4-C-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0001936065950001636
wherein E isxEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; eyEach independently selected from hydrogen atom, alkyl and alkoxy; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001637
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein, the structure represented by the general formula 4-C-1-1 is further preferably selected from the following general structures:
Figure BDA0001936065950001641
wherein E isxEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001642
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
wherein, E in the general formula 4-C-1-1-1xWhen it is a bromine atom, itThe activated structure can react with carboxyl in a system to realize the special effect of strengthening the force-induced crosslinking, and the structure shown in the general formula 4-C-1-1-2 can release hydrogen halide after being activated to realize the change of the force-induced pH value, so the method is more preferable.
A typical structure of the formula 4-C-1-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001643
wherein the content of the first and second substances,
Figure BDA0001936065950001644
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structure represented by the general formula 4-C-1-2 is further preferably selected from the following general structures:
Figure BDA0001936065950001645
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001646
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 4-C-1-2 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001647
wherein the content of the first and second substances,
Figure BDA0001936065950001648
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structure represented by the general formula 4-C-1-3 is further preferably selected from the following general structures:
Figure BDA0001936065950001649
wherein E isxEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom;
Figure BDA00019360659500016410
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
wherein, the five-membered ring at the center can form furyl after the force activation of the general formula 4-C-1-3-1, and can react with other proper groups in the system to realize the special effect of strengthening the force-induced crosslinking.
Typical structures of the general formula 4-C-1-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500016411
Figure BDA0001936065950001651
wherein the content of the first and second substances,
Figure BDA0001936065950001652
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structure represented by the general formula 4-C-1-4 is further preferably selected from the following general structures:
Figure BDA0001936065950001653
among them, the force sensitive groups shown in the general formula 4-C-1-4-2 can react with carboxyl in the system after being activated by force to realize the special effect of force-induced enhancement, and the force sensitive groups shown in the general formula 4-C-1-4-3 can change color after being activated by force to realize the special effect of force-induced color change, so that the method is more preferable.
A typical structure of the formula 4-C-1-4 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001654
wherein the content of the first and second substances,
Figure BDA0001936065950001655
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 4-C-1-5 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001656
wherein the content of the first and second substances,
Figure BDA0001936065950001657
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the alkyne-furan adduct series refers to a force-sensitive group containing alkyne-furan adduct force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0001936065950001658
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0001936065950001659
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 5-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500016510
wherein the content of the first and second substances,
Figure BDA00019360659500016511
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the anthracene-triazoline-dione adduct series refers to a force-sensitive group containing anthracene-triazoline-dione adduct force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA00019360659500016512
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA00019360659500016513
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the anthracene group generated after the force-sensitive group is activated by force has a fluorescence effect, can realize special effects including but not limited to force-induced fluorescence and the like, and is preferably connected with other functional groups with a fluorescence enhancement effect, so that the force-induced fluorescence effect is more remarkable; the triazolinedione group generated after the force-sensitive group is activated by force can be subjected to addition reaction with groups such as diene group and the like, and when R is a substituted polymer chain which does not participate in the force activation or is connected with the triazolinedione group in another force-sensitive group and the system simultaneously contains the groups such as diene group and the like, special effects including but not limited to force-induced chemical reaction, force-induced crosslinking enhancement and the like can be realized, so that the triazolinedione group is also preferable.
A typical structure of the formula 5-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500016514
Figure BDA0001936065950001661
wherein the content of the first and second substances,
Figure BDA0001936065950001662
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the alkynyl series bending activation mechanism refers to a force sensitive group containing alkynyl force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following:
Figure BDA0001936065950001663
wherein the content of the first and second substances,
Figure BDA0001936065950001664
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation; after being bent and activated, the series of force sensitive groups can generate azide-alkyne click reaction without catalysts with azide groups, and special effects including but not limited to force-induced crosslinking and the like are realized.
A typical structure of the formula 5-C-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001665
wherein the content of the first and second substances,
Figure BDA0001936065950001666
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, covalent single force sensitive groups based on other mechanisms include, but are not limited to, the following series: a double nitrite series, a 1, 1' -linked condensed ring series and a bisthiomaleimide series.
In the invention, the covalent single force-sensitive group of the other mechanism of the double-nitrite series refers to a single force-sensitive group containing a double-nitrite force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following groups:
Figure BDA0001936065950001667
wherein X is selected from oxygen atom, sulfur atom, preferably oxygen atom;
Figure BDA0001936065950001668
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain, whether or not participating in force activation, different on the same atom
Figure BDA0001936065950001669
Can be linked to form a ring, on different atoms
Figure BDA00019360659500016610
Or can be connected into a ring. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the structure of the covalent single-force sensitive group of the other mechanism of the double nitrite series can be exemplified as follows:
Figure BDA00019360659500016611
Figure BDA0001936065950001671
wherein the content of the first and second substances,
Figure BDA0001936065950001672
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the invention, the covalent single force sensitive group of other mechanisms of the 1, 1 '-linked condensed ring series refers to a single force sensitive group containing 1, 1' -linked condensed ring force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950001673
wherein each R is independently any suitable atom, substituent, substituted polymer chain;
Figure BDA0001936065950001674
represents an aromatic ring having an arbitrary number of elements.
Figure BDA0001936065950001675
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the structure of the covalent single force sensitive group of the other mechanism of the 1, 1' -linked condensed ring series can be exemplified as follows:
Figure BDA0001936065950001676
wherein the content of the first and second substances,
Figure BDA0001936065950001677
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the covalent single force-sensitive group of the dithiomaleimide series with other mechanisms refers to a single force-sensitive group containing a dithiomaleimide force-sensitive element, and the structural general formula includes but is not limited to the following groups:
Figure BDA0001936065950001678
wherein the content of the first and second substances,
Figure BDA0001936065950001679
an aromatic ring having an arbitrary number of elements;
Figure BDA00019360659500016710
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the structure of the covalent single force sensitive group of the bis-thiolylimide series with other mechanisms can be exemplified as follows:
Figure BDA00019360659500016711
wherein the content of the first and second substances,
Figure BDA00019360659500016712
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the division is performed in a non-covalent complexing manner, and the non-covalent single force-sensitive groups used to generate the complex force-sensitive groups include, but are not limited to, the following groups: non-covalent single force sensitive groups based on supramolecular complexes, non-covalent single force sensitive groups based on supramolecular assemblies, non-covalent single force sensitive groups based on compositions, non-covalent single force sensitive groups based on aggregates. Non-covalent single force-sensitive groups based on a non-covalent single force-sensitive group of supramolecular complexes and a composition of motifs are preferred as force-sensitive components in a complex force-sensitive group for generating complexes containing non-covalent force-sensitive components. The non-covalent single force sensitive group is capable of specifically responding to mechanical forces and producing significant specific force-induced response properties/effects, such as catalytic, optical, spectroscopic, etc. supramolecular interactions.
In the present invention, the non-covalent single force sensitive groups based on supramolecular complexes include, but are not limited to, the following series: coordination bond series, host-guest interaction series, hydrogen bond interaction series and pi-pi stacking interaction series.
In the present invention, non-covalent single force-sensitive groups based on coordination bonds include, but are not limited to, the following sub-series: complexation of unsaturated carbon-carbon bonds with transition metals, carbene-metal coordination bonds, boron-nitrogen coordination bonds, platinum-phosphorus coordination bonds, metallocene coordination bonds, ligand-lanthanide metal ion complexation, and pincer-like compound coordination bonds.
In the present invention, the non-covalent single force sensitive group of the complexation of the unsaturated carbon-carbon bond and the transition metal refers to a single force sensitive group containing a complexation force sensitive element of the unsaturated carbon-carbon bond and the transition metal, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0001936065950001681
wherein the content of the first and second substances,
Figure BDA0001936065950001682
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each R is independently any suitable atom, substituent, substituted polymer chain; in different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
The unsaturated carbon-carbon bond of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001683
Figure BDA0001936065950001691
wherein the content of the first and second substances,
Figure BDA0001936065950001692
an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1;
Figure BDA0001936065950001693
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001694
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-1) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001695
Figure BDA0001936065950001701
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-2) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001702
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-2) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001703
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001704
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-3) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001705
The complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001706
Figure BDA0001936065950001711
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001712
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001713
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-5) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001714
Figure BDA0001936065950001721
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001722
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-6) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001723
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001724
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-7) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001725
Figure BDA0001936065950001731
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-8) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001732
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-8) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001733
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-9) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001741
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-9) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001742
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-10) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001743
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-10) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001744
the structure of the complex of the unsaturated carbon-carbon bond having the general structural formula (A-11) and the transition metal of the present invention is exemplified by the following:
Figure BDA0001936065950001745
in the invention, the non-covalent single force sensitive group of the carbene-metal coordination bond refers to a single force sensitive group containing a carbene-metal coordination bond force sensitive element, and the structural general formula of the single force sensitive group includes but is not limited to the following types:
Figure BDA0001936065950001751
wherein the content of the first and second substances,
Figure BDA0001936065950001752
the selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, the carbene-metal coordination bond, carbene ligand, is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001753
wherein, X4Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C- (R)2Preferably from an oxygen atom;
Figure BDA0001936065950001754
the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.
In the invention, the non-covalent single force sensitive group of the carbene-metal coordination bond refers to a single force sensitive group containing a carbene-metal coordination bond force sensitive element, wherein the structural general formula of the carbene includes but is not limited to the following types:
Figure BDA0001936065950001755
wherein the content of the first and second substances,
Figure BDA0001936065950001756
the selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, the carbene-metal coordination bond, carbene ligand, is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001757
wherein, X4、
Figure BDA0001936065950001758
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the carbene-metal coordination bond having the general structural formulas (B-1), (B-2), (B-3) and (B-4) can be selected from, but not limited to, the following structures:
Figure BDA0001936065950001759
Figure BDA0001936065950001761
wherein, X4、
Figure BDA0001936065950001762
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted; m is a metal center, which may be any suitable ionic form, compound/chelate form, and combinations thereof, of any one of the transition metals; .
In the present invention, the carbene-metal coordination bond having the general structural formulae (B-1), (B-2), (B-3) and (B-4) has the following structure:
Figure BDA0001936065950001763
Figure BDA0001936065950001771
wherein, X4、M、
Figure BDA0001936065950001772
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the non-covalent single force-sensitive group of boron-nitrogen coordination bond refers to a single force-sensitive group containing a force-sensitive element of boron-nitrogen coordination bond, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0001936065950001773
wherein the content of the first and second substances,
Figure BDA0001936065950001774
the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.
The boron-nitrogen coordination bond of the present invention, formula (C-1), may further preferably be selected from, but not limited to, at least one of the following structures:
Figure BDA0001936065950001775
wherein the content of the first and second substances,
Figure BDA0001936065950001776
r, n, the ranges of choice are as previously described in the series of force-sensitive clusters and will not be further described herein;
Figure BDA0001936065950001777
represents any number of nitrogen heterocycles, including but not limited to aliphatic nitrogen heterocycles, aromatic nitrogen heterocycles, and combinations thereof.
In the present invention, said boron-nitrogen coordination bond having the general structural formula (C-1) is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001778
in the present invention, the boron-nitrogen coordination bond having the general structural formula (C-1) is exemplified by the following structures:
Figure BDA0001936065950001779
in the present invention, the non-covalent single force-sensitive group of platinum-phosphorus coordination bond refers to a single force-sensitive group containing platinum-phosphorus coordination bond force-sensitive elements therein, and the structural formula thereof includes but is not limited to the following types:
Figure BDA00019360659500017710
wherein, X5Each independently selected from a chlorine atom, a bromine atom, an iodine atom, preferably from a chlorine atom;
Figure BDA0001936065950001781
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following subclasses:
Figure BDA0001936065950001782
wherein, X5、
Figure BDA0001936065950001783
The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following structures:
Figure BDA0001936065950001784
wherein, X5、
Figure BDA0001936065950001785
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the structure of the platinum-phosphorus coordination bond having the general structural formula (D-1) is exemplified as follows:
Figure BDA0001936065950001786
in the present invention, the non-covalent single force-sensitive group of metallocene coordination bond refers to a single force-sensitive group containing a force-sensitive element of metallocene coordination bond, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0001936065950001787
wherein, M is a metal center,
Figure BDA0001936065950001788
is a ligand of cyclopentadiene and a ligand of cyclopentadiene,
Figure BDA0001936065950001789
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted. The metal centers are preferably metals of the first to seventh subgroups and of the eighth group. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). The metal center is more preferably a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), a metal of the actinide series (Th). More preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb or Th, and still more preferably Fe, Co or Ni.
In the present invention, the metallocene coordination bond having the general structural formula (E-1) is exemplified by the following structures:
Figure BDA00019360659500017810
Figure BDA0001936065950001791
wherein the content of the first and second substances,
Figure BDA0001936065950001792
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the invention, the non-covalent single force sensitive group of ligand-lanthanide metal ion complexation refers to a single force sensitive group containing a ligand-lanthanide metal ion complexation force sensitive element, and the single force sensitive group can change the position of the ligand group more easily when being stressed, thereby showing obvious stress response properties, including changes of fluorescence, color and the like.
In embodiments of the present invention, suitable ligand groups may be exemplified by, but are not limited to:
Figure BDA0001936065950001793
in an embodiment of the invention, the lanthanide metal includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; preferably lanthanide series Ce, Eu, Tb, Ho, Tm, Lu; more preferably Ce, Eu, Tb, to obtain more remarkable stress responsiveness.
In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950001794
Figure BDA0001936065950001801
in the present invention, the non-covalent single force-sensitive group of the pincer compound coordination bond refers to a single force-sensitive group containing a force-sensitive element of the pincer compound coordination bond, and the structure of the single force-sensitive group can be exemplified as follows:
Figure BDA0001936065950001802
in the present invention, the non-covalent single force sensitive groups based on supramolecular assemblies include, but are not limited to, the following series: the dye molecule series non-covalent single force sensitive group comprises a donor-acceptor series, a diketopyrrolopyrrole series, a conjugated series, a platinum coordination series, a gold coordination series, a beryllium coordination series, a copper coordination series, an iridium coordination series, a boron coordination series, a phenothiazine series, a dioxaborolane series and a dye molecule series.
In the present invention, the non-covalent single force-sensitive group of the donor-acceptor series refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by a donor-acceptor self-assembly element, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0001936065950001803
wherein, W4Is an atom or group having an electron withdrawing effect; wherein, the atom with electron-withdrawing effect is selected from but not limited to oxygen atom or sulfur atom, preferably oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:
Figure BDA0001936065950001804
wherein Ar is7、Ar8Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a polycyclic structure or a fused ring structure; by way of example, suitable Ar' s7、Ar8Selected from, but not limited to:
Figure BDA0001936065950001805
wherein the content of the first and second substances,
Figure BDA0001936065950001806
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula F-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001811
wherein the content of the first and second substances,
Figure BDA0001936065950001812
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula F-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001813
wherein the content of the first and second substances,
Figure BDA0001936065950001814
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula F-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001815
wherein the content of the first and second substances,
Figure BDA0001936065950001816
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the diketopyrrolopyrrole series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by diketopyrrolopyrrole self-assembly elements, and the structural general formula of the non-covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950001821
wherein the content of the first and second substances,
Figure BDA0001936065950001822
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula G-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001823
wherein the content of the first and second substances,
Figure BDA0001936065950001824
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the conjugated series of non-covalent single force-sensitive groups refer to force-sensitive groups containing self-assembled aggregate force-sensitive elements formed by conjugated self-assembled elements; wherein, the conjugated self-assembly motif includes but is not limited to the following subseries: polydiacetylene series, polydiphenylacetylene series, polythiophene series, polypyrrole series, anthraquinone series, polyfluorene series, oligomeric p-phenylene vinylene series, bis (benzoxazole) stilbene series, and aza-condensed ring sub-series self-assembly motif.
Wherein, the structural general formula of the polydiacetylene subunit self-assembly unit includes but not limited to the following types:
Figure BDA0001936065950001825
wherein n is the number of the repeating units, and the value range of n is an integer greater than 2, preferably an integer greater than or equal to 5, and more preferably an integer greater than or equal to 10;
Figure BDA0001936065950001826
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001827
wherein n and p are the number of the repeating units, and the value ranges thereof are respectively independent integers more than 2, preferably more than or equal to 5, and more preferably more than or equal to 10;
Figure BDA0001936065950001828
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the polydiphenylacetylene self-assembly motif comprises but is not limited to the following types:
Figure BDA0001936065950001829
wherein n is,
Figure BDA00019360659500018210
The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.
A typical structure of the formula H-2 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001831
wherein n, n1、n2The number of the repeating units is an integer which is greater than 2, preferably greater than or equal to 5, and more preferably greater than or equal to 10;
Figure BDA0001936065950001832
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the sub-series self-assembly motif of the polythiophene comprises but is not limited to the following classes:
Figure BDA0001936065950001833
wherein n is the number of the repeating units and the value range of n is an integer larger than 5;
Figure BDA0001936065950001834
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001835
wherein n, n1、n2The number of repeating units is an integer in the range of greater than 5.
Wherein, the structural general formula of the self-assembly motif of the polypyrrolidine series includes but is not limited to the following classes:
Figure BDA0001936065950001836
wherein n is,
Figure BDA0001936065950001837
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-4 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001838
wherein n, n1、n2The number of repeating units is an integer with a value range of more than 5;
Figure BDA0001936065950001839
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly motif of the anthraquinone sub-series includes but is not limited to the following classes:
Figure BDA00019360659500018310
wherein n is,
Figure BDA00019360659500018311
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-5 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500018312
wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-5;
Figure BDA00019360659500018313
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the polyfluorenesub-series self-assembly motif includes but is not limited to the following classes:
Figure BDA00019360659500018314
wherein n is,
Figure BDA00019360659500018315
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-6 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001841
wherein n, n1、n2The number of the repeating units is defined, and the value ranges of the repeating units are respectively independent integers more than 5;
Figure BDA0001936065950001842
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly unit of the oligomeric p-phenylene vinylene subunit includes but is not limited to the following types:
Figure BDA0001936065950001843
wherein n is,
Figure BDA0001936065950001844
The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.
A typical structure of the formula H-7 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001845
wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-7;
Figure BDA0001936065950001846
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the bis (benzoxazole) stilbene sublines self-assembly motif includes but is not limited to the following classes:
Figure BDA0001936065950001847
wherein the content of the first and second substances,
Figure BDA0001936065950001848
selected from, but not limited to, at least one of the following structures:
Figure BDA0001936065950001849
Figure BDA00019360659500018410
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-8 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500018411
wherein the content of the first and second substances,
Figure BDA00019360659500018412
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly motif of the aza-condensed ring sub-series includes but is not limited to the following types:
Figure BDA00019360659500018413
wherein the content of the first and second substances,
Figure BDA00019360659500018414
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-9 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500018415
wherein the content of the first and second substances,
Figure BDA0001936065950001851
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the platinum coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by platinum coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0001936065950001852
wherein each V is independently selected from a carbon atom or a nitrogen atom;
wherein Lg is1Is a monodentate ligand coordinated to the platinum atom; wherein the monodentate ligand is selected from, but not limited to: a halogen atom,
Figure BDA0001936065950001853
Figure BDA0001936065950001854
Wherein Lg is2Is a monodentate ligand coordinated to the platinum atom; each Lg2Are the same or different; wherein the monodentate ligand is selected from, but not limited to:
Figure BDA0001936065950001855
wherein the content of the first and second substances,
Figure BDA0001936065950001856
is a bidentate ligand with V and nitrogen atoms as coordinating atoms; by way of example, the bidentate ligand is selected from, but not limited to:
Figure BDA0001936065950001857
wherein the content of the first and second substances,
Figure BDA0001936065950001858
is a tridentate ligand with V and nitrogen atoms as coordination atoms; by way of example, the tridentate ligand is selected from, but not limited to:
Figure BDA0001936065950001859
wherein the content of the first and second substances,
Figure BDA00019360659500018510
is a tetradentate ligand taking V and nitrogen atoms as coordination atoms; by way of example, the tetradentate ligand is selected from, but not limited to:
Figure BDA00019360659500018511
wherein the content of the first and second substances,
Figure BDA00019360659500018512
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae I-1 to I-4 may be illustrated below, but the present invention is not limited thereto:
Figure BDA00019360659500018513
Figure BDA0001936065950001861
wherein the content of the first and second substances,
Figure BDA0001936065950001862
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the gold coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by gold coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0001936065950001863
wherein Lg is3Is a monodentate ligand coordinated to a gold atom; each Lg3Are the same or different; wherein the monodentate ligand is selected from, but not limited to:
Figure BDA0001936065950001864
wherein the content of the first and second substances,
Figure BDA0001936065950001865
indicates that n is connected with
Figure BDA0001936065950001866
Wherein n is 0, 1 or an integer greater than 1; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited and is selected from, but not limited to, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom; the hydrogen atoms on the ring-forming atoms may be substituted with any suitable substituent atom or substituent; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. By way of example, those that are suitable
Figure BDA0001936065950001867
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001868
wherein the content of the first and second substances,
Figure BDA0001936065950001869
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula (I-2);
wherein the content of the first and second substances,
Figure BDA00019360659500018610
is a bidentate ligand with a sulfur atom and a nitrogen atom as coordination atoms; by way of example, those that are suitable
Figure BDA00019360659500018611
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001871
wherein the content of the first and second substances,
Figure BDA0001936065950001872
is a bidentate ligand taking a phosphorus atom as a coordination atom, wherein, the metal atoms coordinated with phosphine can be the same gold atom or different gold atoms; by way of example, those that are suitable
Figure BDA0001936065950001873
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001874
wherein the content of the first and second substances,
Figure BDA0001936065950001875
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of formulae J-1 to J-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001876
Figure BDA0001936065950001881
wherein the content of the first and second substances,
Figure BDA0001936065950001882
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the beryllium coordinated series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembled aggregate force-sensitive elements formed by beryllium coordinated self-assembled elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950001883
wherein the content of the first and second substances,
Figure BDA0001936065950001884
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula K-1 can be illustrated as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001885
wherein the content of the first and second substances,
Figure BDA0001936065950001886
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the copper coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by copper coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0001936065950001887
wherein the content of the first and second substances,
Figure BDA0001936065950001888
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula L-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001889
wherein the content of the first and second substances,
Figure BDA00019360659500018810
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the iridium coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by iridium coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950001891
wherein the content of the first and second substances,
Figure BDA0001936065950001892
is a bidentate ligand with carbon atoms and nitrogen atoms as coordination atoms; by way of example, those that are suitable
Figure BDA0001936065950001893
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001894
wherein the content of the first and second substances,
Figure BDA0001936065950001895
is a bidentate ligand with nitrogen atoms as coordination atoms; by way of example, those that are suitable
Figure BDA0001936065950001896
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001897
wherein the content of the first and second substances,
Figure BDA0001936065950001898
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula M-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001899
wherein the content of the first and second substances,
Figure BDA00019360659500018910
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the boron coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by boron coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA00019360659500018911
wherein, R is respectively and independently selected from halogen atom, cyano-group and C1-10Hydrocarbyl/heterohydrocarbyl, substituted C1-10Hydrocarbyl/heterohydrocarbyl; r is preferably selected from halogen atoms, phenyl, pentafluorophenyl; v, V' are each independently selected from an oxygen atom or a nitrogen atom;
Figure BDA00019360659500018912
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, of any two of the same general formula
Figure BDA00019360659500018913
With or without looping.
Wherein the structures represented by the general formulae N-1 to N-5 are preferably selected from at least a subset of the following general structures:
Figure BDA00019360659500018914
wherein the content of the first and second substances,
Figure BDA0001936065950001901
is an aromatic ring; the ring structure of the aromatic ring is selected fromMonocyclic structure, polycyclic structure, condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the content of the first and second substances,
Figure BDA0001936065950001902
to connect n
Figure BDA0001936065950001903
The ring-forming atoms of the ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms; wherein the content of the first and second substances,
Figure BDA0001936065950001904
to connect n
Figure BDA0001936065950001905
At least one of the ring-forming atoms of the nitrogen-containing aromatic heterocyclic ring is a nitrogen atom, the nitrogen-containing aromatic heterocyclic ring forms a coordinate bond with a boron atom through the nitrogen atom, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms; wherein the content of the first and second substances,
Figure BDA0001936065950001906
to connect n
Figure BDA0001936065950001907
At least two of the ring-forming atoms of (1) are carbon atoms, and the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; wherein the content of the first and second substances,
Figure BDA0001936065950001908
to connect n
Figure BDA0001936065950001909
At least two of the ring-forming atoms of the nitrogen-containing aromatic heterocyclic ring of (1) are nitrogen atoms, and one of the nitrogen atoms forms a coordinate bond with a boron atom, which is a nitrogen-containing aromatic heterocyclic ringThe remaining ring atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms;
wherein R, V, V
Figure BDA00019360659500019010
The definitions, selection ranges and preferred ranges of the general formulas N-1 to N-5 are the same.
Typical structures of the formulae N-1 to N-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500019011
Figure BDA0001936065950001911
wherein the content of the first and second substances,
Figure BDA0001936065950001912
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the phenothiazine series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive units formed by phenothiazine self-assembly units; wherein, the phenothiazine self-assembly motif comprises but is not limited to the following classes:
Figure BDA0001936065950001913
wherein each R is independently selected from the group consisting of atoms (including hydrogen atoms), substituents, and substituted polymer chains that may or may not participate in force activation; wherein said substituent atoms are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom; the substituent is preferably selected from substituents with electron-withdrawing effect, so that the intermolecular stacking effect is enhanced, and more remarkable force-induced responsiveness is obtained; wherein said substituents having electron withdrawing effect include but are not limited to: trifluoromethyl, trichloromethyl, nitro, cyano, sulfonic group, aldehyde group, alkyl acyl, alkoxy acyl, carboxyl, amide group;
wherein n is the total number of substituent atoms, substituents, and substituted polymer chains linked to the atoms constituting the ring structure, and is 0, 1, or an integer greater than 1; when n is more than 1, the structures of the R can be the same or different;
wherein the content of the first and second substances,
Figure BDA0001936065950001914
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae O-1, O-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001915
wherein the content of the first and second substances,
Figure BDA0001936065950001916
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the dioxaborolane series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by self-assembly elements of the dioxaborolane, and the structural general formula of the non-covalent single force-sensitive group comprises the following groups:
Figure BDA0001936065950001917
wherein Ar is9Is an aromatic ring having an electron donating effect; wherein the aromatic ring is a polycyclic structure selected from, but not limited to:
Figure BDA0001936065950001918
wherein the content of the first and second substances,
Figure BDA0001936065950001919
each independently and optionally in combinationSuitable atoms (including hydrogen atoms), substituents, and substituted polymer chains that may or may not participate in force activation.
A typical structure of the formula P-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001921
wherein the content of the first and second substances,
Figure BDA0001936065950001922
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the dye molecule series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by dye molecule self-assembly elements; wherein, the dye molecule self-assembly motif is selected from one of the following structural formulas:
Figure BDA0001936065950001923
wherein the hydrogen atoms on the dye molecules may be substituted or unsubstituted by any suitable atom, substituent, polymer chain; and the dye molecules are linked to the polymer or supramolecular polymer chains by suitable means.
By way of example, the structure of a typical self-assembly motif of a dye molecule is shown below, but the invention is not limited thereto:
Figure BDA0001936065950001924
wherein the content of the first and second substances,
Figure BDA0001936065950001925
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, non-covalent, single force-sensitive groups based on aggregates include, but are not limited to, the following series: divinylanthracene series, tetraarylethylene series, cyanoethylene series, berberine series, maleimide series, 4-hydropyran series non-covalent single force sensitive groups.
In the invention, the divinylanthracene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by divinylanthracene aggregation-induced emission elements, and the general structural formula of the group includes but is not limited to the following types:
Figure BDA0001936065950001931
wherein Ar is1、Ar2Each independently selected from aromatic rings, the ring structure of which is selected from monocyclic structure, polycyclic structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
Figure BDA0001936065950001932
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae Q-1 to Q-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001933
wherein the content of the first and second substances,
Figure BDA0001936065950001934
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the non-covalent single force-sensitive group of the tetraarylethylene series refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by tetraarylethylene aggregation-induced emission elements, and the structural general formula includes but is not limited to the following classes:
Figure BDA0001936065950001935
Figure BDA0001936065950001941
wherein, W1Is a divalent linking group, each of which is independently selected from a direct bond, a,
Figure BDA0001936065950001942
Wherein Ar is3Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; wherein the substituted atom, the substituent, the substituted polymer chain are not particularly limited; in order to increase steric hindrance and aggregation-induced emission of the luminescent moiety in a non-planar conformation, and to form loosely-packed aggregates, so as to obtain a more significant force-induced response effect, the ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be adjusted in a large range can be obtained, and the use requirements of various application scenes can be met; in order to increase the intramolecular charge transfer property and obtain a more significant force-induced response effect, particularly a force-induced response effect with a significant change in fluorescence wavelength shift and a high force-induced color contrast, it is more preferable that the substituent on the aromatic ring structure is a substituent having a strong electron-donating effect or electron-withdrawing effect;
wherein the content of the first and second substances,
Figure BDA0001936065950001943
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae R-1 to R-7 may be illustrated below, but the invention is not limited thereto:
Figure BDA0001936065950001944
Figure BDA0001936065950001951
Figure BDA0001936065950001961
wherein the content of the first and second substances,
Figure BDA0001936065950001962
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the cyanoethylene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by cyanoethylene aggregation-induced emission elements, and the structural general formula of the group includes but is not limited to the following classes:
Figure BDA0001936065950001963
wherein Ar is4Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; the substituent atom, substituent group, and substituted polymer chain are not particularly limited. To increaseSteric hindrance and aggregation-induced emission of luminescent moieties in a non-planar conformation to form loosely-packed aggregates to achieve a more significant force-induced response effect, preferably the ring structure of the aromatic ring is a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be regulated in a large range can be obtained, and the application requirements of various application scenes can be met; in order to obtain more significant force-responsive effects, especially force-responsive effects with significant shift in fluorescence wavelength and high color contrast of force-induced discoloration, it is preferred that a portion of the hydrogen atoms on the aromatic ring be substituted with a heteroatom, a hydrocarbyl substituent, or a heteroatom substituent, by way of example, suitable heteroatoms, hydrocarbyl substituents, heteroatom substituents are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, pentafluorothio group, nitro group, cyano group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20Alkylamino radical, C1-20Aryloxy radical, C1-20Arylthio radical, C1-20An arylamine group. Ar is4Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001964
by way of example, typical Ar4Including but not limited to one or more of the following structures:
Figure BDA0001936065950001965
wherein Ar is5Is a divalent aromatic ring, the structure of which is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-constituting atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms bonded to the ring-constituting atoms are optionally substituted by any suitable atom, substituent, group,Substituted polymer chains are substituted or unsubstituted; wherein the substituent atom is preferably selected from fluorine atom, chlorine atom, bromine atom and iodine atom, and the substituent group is preferably selected from C1-20Alkyl radical, C1-20Aryl radical, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20Alkylamino radical, C1-20Aryloxy radical, C1-20Arylthio radical, C1-20An arylamine group. Ar is5Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0001936065950001971
by way of example, typical Ar5Including but not limited to one or more of the following structures:
Figure BDA0001936065950001972
wherein the content of the first and second substances,
Figure BDA0001936065950001973
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula S-1 is further preferably selected from the following general structures:
Figure BDA0001936065950001974
wherein Ar is4、
Figure BDA0001936065950001975
The definition, selection range and preferable range of (A) are the same as those of the general formula S-1.
Typical structures of the formulae S-1 to S-4 may be illustrated below, but the invention is not limited thereto:
Figure BDA0001936065950001976
Figure BDA0001936065950001981
wherein the content of the first and second substances,
Figure BDA0001936065950001982
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the berberine series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by berberine aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0001936065950001991
wherein a is an integer of 1-5, preferably 1 or 2;
wherein the content of the first and second substances,
Figure BDA0001936065950001992
indicates that n is connected with
Figure BDA0001936065950001993
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group, preferably from substituent group with electron-donating effect;
wherein the content of the first and second substances,1r is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when in use1When R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect;
wherein the content of the first and second substances,
Figure BDA0001936065950001994
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula T-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950001995
wherein the content of the first and second substances,
Figure BDA0001936065950001996
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the maleimide series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive element formed by maleimide aggregation-induced emission element, and its structural general formula includes but is not limited to the following classes:
Figure BDA0001936065950001997
wherein the content of the first and second substances,2r is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when in use2When R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect; by way of example, said atoms or substituents having an electron-withdrawing effect are selected from, but not limited to: halogen atom, nitro group, pentafluorothio group, trifluoromethyl group, 4-trifluoromethyl-phenyl group;
wherein the content of the first and second substances,
Figure BDA0001936065950001998
indicates that n is connected with
Figure BDA0001936065950001999
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;
wherein the content of the first and second substances,
Figure BDA00019360659500019910
indicates that n is connected with
Figure BDA00019360659500019911
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;
wherein the content of the first and second substances,
Figure BDA00019360659500019912
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae U-1, U-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00019360659500019913
wherein the content of the first and second substances,
Figure BDA00019360659500019914
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the 4-hydropyran series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by 4-H pyran aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA0001936065950002001
wherein, W2Each independently is a divalent linking group, each independently selected from
Figure BDA0001936065950002002
Wherein, W3Each independently an atom or group having an electron withdrawing effect, preferably from an oxygen atom or a sulfur atom, more preferably from an oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:
Figure BDA0001936065950002003
wherein Ar is6Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a monocyclic structure, a polycyclic structure or a condensed ring structure; by way of example, suitable Ar' s6Selected from, but not limited to:
Figure BDA0001936065950002004
wherein the content of the first and second substances,
Figure BDA0001936065950002005
each independently attached to any suitable hydrogen atom, substituent group, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae V-1 to V-3 may be illustrated below, but the invention is not limited thereto:
Figure BDA0001936065950002006
wherein the content of the first and second substances,
Figure BDA0001936065950002007
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the non-covalent single force sensitive group based on the energy transfer composition refers to a non-covalent force response element formed by combining a non-mechanical force responsive energy donor and a non-mechanical force responsive energy acceptor which can transfer energy with each other, wherein the energy donor and the energy acceptor are respectively not responded by mechanical force, and when mechanical force is acted, the distance, arrangement form and the like between the energy donor and the energy acceptor are changed, so that the energy transfer process between the energy donor and the energy acceptor is weakened/inhibited or enhanced/promoted, and the fluorescence wavelength shift, fluorescence intensity enhancement or weakening, fluorescence lifetime extension or shortening and the like generated by the change show specific force response.
In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; in another case, when the energy donor emits light, energy transfer to the adjacent energy acceptor is achieved through dipole resonance interaction between the energy donor and the energy acceptor. In order to achieve energy transfer between the energy donor and the energy acceptor to achieve the desired force-induced response effect, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) The energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.
In the present invention, the energy donor in the non-covalent single force sensitive moiety of the energy transfer composition may be selected from non-mechanical force responsive fluorophores and/or luminophores, and the energy acceptor may be selected from non-mechanical force responsive fluorophores and/or quenchers.
In the present invention, the energy donor and the energy acceptor contained in the non-covalent single force sensitive group of the energy transfer composition may be selected from the group consisting of, but not limited to, pre-existing, photo-activated, thermal-activated, electro-activated, chemical-activated, bio-activated, magnetic-activated moieties, and does not include force-activated moieties. In the present invention, when multiple energy donors and multiple energy acceptors are contained in the same polymer, each of the energy donors and energy acceptors can have more than one source. In a preferred embodiment of the present invention, all energy donors and energy acceptors are pre-existing, which facilitates force-induced activation by controlling mechanical force action alone, resulting in rapid and stable force-induced response; in another preferred embodiment of the invention, the part of the energy donor or energy donor is pre-existing, and the other part of the energy donor and energy acceptor is selected from the group consisting of those generated by photoactivation, those generated by thermal activation, those generated by electrical activation, those generated by chemical activation, those generated by biological activation, those generated by magnetic activation, and thus facilitates the achievement of a force-induced response effect by light control, thermal control, electrical control, chemical stimulation, biological stimulation and mechanical force in a dual or multiple coordinated control; in another preferred embodiment of the present invention, the energy donor and the energy acceptor are selected from one or more of photoactivated, thermoactivated, electroactive, chemically activated, biologically activated and magnetically activated, which is advantageous for obtaining abundant non-mechanical force response and achieving multiple coordinated force-induced response effects with mechanical force control of the composition to meet the needs of various special application scenarios.
In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group of the energy transfer composition may be on the same polymer chain, on different polymer chains, or one of them may be on the polymer chain; wherein the energy donor and the energy acceptor can be linked to the polymer chain by covalent and/or supramolecular interactions. In the embodiment of the present invention, it is preferable that the energy donor and the energy acceptor are spaced from each other by not more than 10nm, and it is more preferable that the energy donor and the acceptor are kept close to each other by supramolecular interaction and spaced from each other by not more than 10 nm. The supramolecular action described herein, which may be any suitable supramolecular action, includes but is not limited to: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding, radical cation dimerization, phase separation, crystallization; under the action of mechanical force, the supermolecule action is destroyed, so that the energy transfer process is changed, and force-induced responsiveness is obtained; furthermore, due to the reversible nature of the supramolecular interaction, the force sensitive group may also be given a reversible, recyclable force-responsive effect.
In the invention, the energy transfer can be organically regulated and controlled by designing, selecting and adjusting the type, the quantity and the combination of the energy donor/the energy donor, so that excellent diversified and cooperatively controlled energy transfer performance and wide application are obtained.
In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group based on the energy transfer composition may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.
In the present invention, the energy transfer in the non-covalent single force sensitive groups based on the energy transfer composition may be of only one stage or may be of multiple stages. When the polymer contains a plurality of fluorophores/luminophores (or precursors thereof), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is taken as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, so that the phenomenon of multi-stage energy transfer is realized. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.
In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is longer than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon that the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregate fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the fluorescence quenching refers to the property that some fluorophores/luminophores are aggregated to generate fluorescence quenching, and the self-quenching phenomenon is generated when the concentration of the fluorophores/luminophores is too large.
In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive, and magnetically activated.
In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from the group consisting of, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.
Among these, the covalent organic fluorophores can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002021
Figure BDA0001936065950002031
among them, the following are examples of the aggregation-induced emission organic fluorophore, but the present invention is not limited thereto:
Figure BDA0001936065950002032
Figure BDA0001936065950002041
the organic fluorophores of the other non-covalent complexes, self-assemblies, aggregates, compositions and various combinations thereof may be selected from any suitable structure. Wherein the composition organic fluorophore may itself be a donor and acceptor composition having energy transfer properties.
Among them, the organometallic fluorophore may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002042
Figure BDA0001936065950002051
among them, the organic element fluorophore may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002052
among them, the biological fluorophore can be exemplified as follows, but the present invention is not limited thereto:
GFP、EGFP、GFP-S65T、BFP、CFP、YFP、EBFP、Azurite、EBFP2、mTagBFP、TagRFP、EYFP、ECFP、Cerulean、mTFP、mTurquoise、mCitrine、mVenus、CyPet、YPet、phiYFP、DsRed、mBanana、 mOrange、dTomato、mTangerine、mStrawberry、mCherry、mKO、GFP-Phe66、Sirius、mPlum、mKate、 mKate2、Katushka、mNeptune、TagRFP657、IFP1.4、T-Sapphire、mAmetrine、mKeima、mLSS-Kate1、 mLSS-Kate2；
the inorganic fluorophores include but are not limited to sulfide fluorophores, aluminate fluorophores, silicate fluorophores, nitride fluorophores, oxide fluorophores, oxynitride fluorophores, rare earth fluorophores, and inorganic non-metal quantum dots, wherein part of the inorganic fluorophores are mainly composed of a substrate: activator composition, inorganic fluorophores may be exemplified as follows, but the invention is not limited thereto:
CaS：Eu、SrS：Ce、SrGa2S4：Eu、SrAl2O4：Ce、CaAl2O4：Eu、BaAl2O4：Ce、Lu3Al5O12：Eu、Y3Al5O12：Ce、 Tb3Al5O12：Ce、Gd3Al5O12：Eu、Ba2SiO4：Eu、Sr2SiO4：Eu、BaSi2O3：Eu、BaSiO3：Eu、Ba3SiO5：Eu、Ba2Si3O8：Eu、 Ba3Si5O13：Eu、Ba9Sc2Si6O24：Eu、Ca3Mg2Si3O12：Ce、Ca3Sc2Si3O12：Ce、Ca2Si2O7：Eu、SrLi2SiO4：Eu、 CaLi2SiO4：Eu、Ca2Si5N8：Eu、Sr2Si5N8：Eu、CaAlSiN3：Eu、ZnO：Eu、ZnO：Li、SrSi2N2O2：Eu、CaSi2N2O2: eu, CdS/ZnS quantum dots, ZnSe/ZnS quantum dots, InP/ZnS quantum dots, CdSe/ZnS quantum dots, carbon quantum dots, PbS quantum dots with emission wavelength in the near infrared region, ZnS: cu series long afterglow material, CaS: bi-series long afterglow material, SrAl2O4: eu, Dy series long afterglow material, CaAl2O4: eu, Nd series long afterglow material, Sr4Al14O25: eu, Dy series long afterglow material, Zn2SiO4: mn, As series long afterglow material, Sr2MgSi2O7: eu, Dy series long afterglow phosphor, Ca2MgSi2O7: eu, Dy series long afterglow material, MgSiO3: mn, Eu, Dy series long afterglow material, CaTiO3: pr, A1 series long afterglow material, Ca8Zn(SiO4)4Cl2: eu series long afterglow phosphor, Ca2Si5N8: eu series long afterglow materials;
inorganic up-converting phosphors typically consist of a host, an activator and a sensitizer, usually doped into nanoparticles or glass by rare earth ions, to absorb long-wavelength radiation and emit short-wavelength fluorescence. Among them, rare earth ions can be exemplified as follows, but the present invention is not limited thereto: scandium ion, yttrium ion, lanthanum ion, cerium ion, neodymium ion, praseodymium ion, promethium ion, europium ion, samarium ion, terbium ion, gadolinium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, lutetium ion, ytterbium ion;
among these, inorganic up-converting fluorophores can be exemplified as follows, but the present invention is not limited thereto:
NaYF4：Er、CaF2：Er、Gd2(MoO4)3：Er、Y2O3：Er、Gd2O2S：Er、BaY2F8：Er、LiNbO3：Er，Yb，Ln、 Gd2O2：Er，Yb、Y3Al5O12：Er，Yb、TiO2：Er，Yb、YF3：Er，Yb、Lu2O3：Yb，Tm、NaYF4：Er，Yb、LaCl3：Pr、 NaGdF4：Yb，
Figure BDA0001936065950002062
core-shell nanostructure, NaYF4：Yb，Tm、Y2BaZnO5：Yb，Ho、NaYF4：Yb，
Figure BDA0001936065950002063
Core-shell nanostructure of Tm, NaYF4：Yb，
Figure BDA0001936065950002064
The core-shell nanostructure of (1).
The organic up-converting fluorophore is preferably an organic composition which achieves up-conversion effect by triplet-triplet annihilation based, said organic composition mainly consisting of a sensitizer and an organic up-converting energy acceptor.
Among them, the following sensitizers can be exemplified, but the present invention is not limited thereto:
Figure BDA0001936065950002061
Figure BDA0001936065950002071
among them, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002072
in the present invention, fluorophores such as organic fluorophores, organic metal fluorophores, organic element fluorophores, biological fluorophores, organic upconversion fluorophores, inorganic fluorophores, and inorganic upconversion fluorophores can also form various noncovalent complexes, self-assemblies, aggregates, and combinations thereof, which can be the same or different.
In the present invention, the fluorophore generated by chemical activation refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a chemical reaction. Suitable structures that can be chemically activated to generate fluorophores can be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be chemically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the fluorescence generated by biological activation refers to a structure having fluorescence in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed in structure by a biological reaction. Suitable bioactivatable fluorophore generating structures may be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores, although the invention is not limited thereto. The various force-sensitive moieties/groups of the invention having force-sensitive properties can also be biologically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the photo-activation generated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a photoreaction. Suitable photoactivatable fluorophore-generating structures can be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores. The following may be exemplified, but the invention is not limited thereto:
PA-GFP (trademark), PA-mCherry1 (trademark), Kaede (trademark), PS-CFP2 (trademark), mEosFP (trademark), Dendra2 (trademark), Dronpa (trademark), rsFasLime (trademark), Pandon (trademark), bsDronpa (trademark), Kindling (trademark).
The force-sensitive moieties/groups of the present invention having force-sensitive properties can also be photoactivated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the thermally activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor of the fluorophore is changed by a structural change due to a thermal reaction. Suitable structures for the heat-activatable fluorophores can be obtained by suitable structural modification and derivatization of the suitable fluorophores mentioned above, but the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be thermally activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the electrically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by structural change of its precursor under the action of an electric stress is changed. Suitable structures that can be electroactive to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be electroactive under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the magnetically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a magnetic reaction. Suitable structures which can be magnetically activated to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be magnetically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the fluorophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable fluorescent moiety and a quencher moiety, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to generate fluorescence from the fluorescent moiety, which may be any suitable entity as described above that can generate fluorescence upon excitation with light of a suitable wavelength.
In the present invention, the fluorophore may function as an energy donor under suitable conditions and may function as an energy acceptor under otherwise suitable conditions. By rational utilization of the fluorophores, a desirable combination of energy donors and acceptors can be obtained, resulting in excellent energy transfer properties.
In the present invention, the luminophore may be selected from, but not limited to, chemical activation generated, biological activation generated, photoactivation generated/photoluminescent, thermoactivation generated/thermoluminescable, electroactive generated/electroluminescent, magnetic activation generated/magnetoluminesceable.
In the present invention, the precursor of the luminophore generated by the chemical activation is called a chemiluminescent group, which refers to a chemical group capable of generating a luminescence phenomenon by a structural change after a chemical reaction, and includes, but is not limited to, a suitable dioxetane chemiluminescent system, a luminol chemiluminescent system, an oxalate peroxide chemiluminescent system, an acidic potassium permanganate chemiluminescent system, a tetravalent cerium chemiluminescent system, an acridinium ester chemiluminescent system, and a fluorescein chemiluminescent system.
Wherein the suitable dioxetane chemiluminescent system is comprised of a suitable dioxetane compound and a fluorescer, wherein the suitable dioxetane compound may be exemplified by, but is not limited to:
Figure BDA0001936065950002091
among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:
5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;
the luminol chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002092
the oxalate peroxide chemiluminescence system comprises an oxalate compound, a fluorescent agent and hydrogen peroxide, wherein the oxalate compound can be exemplified as follows, but the invention is not limited to the following:
Figure BDA0001936065950002093
among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:
5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;
the chemiluminescence system of the acidic potassium permanganate consists of acidic potassium permanganate and a substance to be detected, and some adaptive compounds can be added to enhance the chemiluminescence intensity of the acidic potassium permanganate4Test substance or acidic KMnO4- (luminescence enhancer) -analyte, which may be exemplified as follows, but the present invention is not limited thereto:
acidic KMnO4Oxalate, acidic KMnO4Luminol, acidic KMnO4- (divalent lead ion) -luminol, acidic KMnO4-SO2Acidic KMnO4Sulfite, acidic KMnO4Glutamic acid, acidic KMnO4Aspartic acid, acidic KMnO4- (Formaldehyde) -L-Tryptophan, acidic KMnO4- (Formaldehyde) -methotrexate, acidic KMnO4- (Formaldehyde) -Dichloromethabenzuron, acidic KMnO4- (Formaldehyde) -Aminopyrine, acidic KMnO4- (Formaldehyde) -iodine, acidic KMnO4- (Formaldehyde) -tyrosine, acidic KMnO4- (glyoxal) -imipramine, acidic KMnO4- (glyoxal) -dipyridamole, acidic KMnO4- (glyoxal) -reserpine, acidic KMnO4- (sodium dithionite) -riboflavin, acidic KMnO4- (sodium dithionite) -tetrahydropalmatine, acidic KMnO4- (sodium dithionite) -vitamin B6Acidic KMnO4- (sodium dithionite) -pipemidic acid, acidic KMnO4Morphine, acidic KMnO4-buprenorphine, acidic KMnO4-para-aminobenzoate, acidic KMnO4Codeine, acidic KMnO4Tryptophan, acidic KMnO4Dopamine, acidic KMnO4Levodopa, acidic KMnO4Adrenaline, acidic KMnO4-methoxybenzylaminopyridine, acidic KMnO4-DL-malic acid;
the tetravalent cerium chemiluminescence system is composed of tetravalent cerium and a test object, and some adaptive compounds can be added to enhance the chemiluminescence intensity, and in the invention, the tetravalent cerium chemiluminescence system is expressed as a tetravalent cerium-test object or a tetravalent cerium- (luminescence enhancer) -test object, which can be exemplified as follows, but the invention is not limited thereto:
tetravalent cerium-paracetamol, tetravalent cerium-naproxen, tetravalent cerium-phenacetin, tetravalent cerium-biphenyltriphenol, tetravalent cerium-sulfite, tetravalent cerium- (quinine) -penicillamine, tetravalent cerium- (quinine) -2-mercaptoethane sulfonate, tetravalent cerium- (quinine) -cysteine, tetravalent cerium- (quinine) -thiazole Schiff base, tetravalent cerium- (quinine) -sulfite, tetravalent cerium- (cinchonine) -sulfite, tetravalent cerium- (ciprofloxacin) -sulfite, tetravalent cerium- (oxrofloxacin) -sulfite, tetravalent cerium- (oxfloxacin) -sulfite, tetravalent cerium- (oxpocetine) -sulfite, pentamidine-or-morpholine-containing compound, and mixtures thereof,Tetravalent cerium- (norfloxacin) -sulfite, tetravalent cerium- (sipafloxacin) -sulfite, tetravalent cerium- (roxofloxacin) -sulfite, quaternary cerium- (roxofloxacin) -sulfite,
Figure BDA0001936065950002104
Figure BDA0001936065950002103
Tetravalent cerium- (N-tetrahydrobenzothiazole imine Schiff base) -sulfite, tetravalent cerium-rhodamine 5G, tetravalent cerium- (rhodamine B) -folic acid, tetravalent cerium- (rhodamine B) -ascorbic acid;
among them, the acridinium ester chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002101
4- (2-succinimidylcarbonyl) phenyl-10-methylacridine-9-carboxylate fluorosulfonate;
the fluorescein chemiluminescence system can be exemplified as follows, but the invention is not limited to the following:
Figure BDA0001936065950002102
in the present invention, the biologically-activated luminophore, a precursor thereof, is referred to as a biologically-activatable luminophore, which refers to a chemical or biological group that is capable of undergoing a structural change by a biological reaction (e.g., catalysis by a biological enzyme) to produce a luminescence phenomenon. The bioactivated luminescence may be exemplified as follows, but the present invention is not limited thereto: marine animal luminescence, bacterial luminescence, firefly luminescence; wherein the marine animals are luminous, including but not limited to luminous marine animals such as noctiluca, dinoflagellate, radioworms, jellyfish, sea feathers, ctenopharyngodon idellus, multicastoma, krill, cerasus, cephalopods, echinoderm, tunicates, fish, clamworm, sea bamboo shoot, sea worm, copepods, schizothorax, Phillips longifolus, columna gigas and the like; the bacteria emit light, and the bacteria include but are not limited to luminescent heterobrevibacterium, luminous bacillus leiognathi, Shewanella villosa, alteromonas haiensis, Vibrio harveyi, Vibrio livialis biotype I, Vibrio fischeri, Vibrio paradoxus, Vibrio orientalis, Vibrio mediterranei, Vibrio arctica, Vibrio cholerae, Vibrio qinghai and the like; the firefly luminescence includes but is not limited to fluorescein bioluminescence and dioxetane bioluminescence.
In the present invention, the photo-activation generated/photo-luminescent luminophore and its precursor are called photo-activation luminophores, which refer to chemical groups that can undergo a structural change after a photo-reaction, thereby generating a luminescence phenomenon.
In the present invention, the thermally activated/thermoluminescable luminophore precursor thereof is referred to as a thermoactivatable luminophore, which refers to a chemical group that is capable of undergoing a structural change upon thermal reaction, thereby generating a luminescence phenomenon.
In the present invention, the electroactive produced/electroluminescent luminophore and its precursor are referred to as an electroactive luminophore, which means a chemical group that can generate a luminescence phenomenon by a structural change or charge/hole combination or electrical excitation after an electrochemical reaction. Examples thereof may be as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002111
in the present invention, the electrically activatable luminophores further comprise organic light emitting diodes and inorganic light emitting diodes. Wherein, the organic light emitting diode includes, but not limited to, an organic small molecule light emitting diode and an organic polymer light emitting diode; wherein the electron transport layer material in the organic small molecule light emitting diode can be selected from fluorescent dye compounds such as Alq, Znq, Gaq, Bebq, Balq, DPVBi, ZnSPB, PBD, OXD, BBOT, etc.; the material of the hole transport layer is selected from, but not limited to, aromatic amine fluorescent compounds, such as organic materials like TPD, TDATA, etc. Organic polymer light emitting diodes include, but are not limited to: organic electroluminescent materials such as poly (p-phenylenes), poly (acetylenes), poly (carbazoles), polyfluorenes, and polythiophenes. Wherein, the inorganic light emitting diode material includes but not limited to: gallium arsenide light emitting diodes, gallium phosphide light emitting diodes, silicon carbide light emitting diodes, gallium nitride light emitting diodes, zinc selenide light emitting diodes, gallium phosphide light emitting diodes, aluminum arsenide light emitting diodes.
In the present invention, the magnetically activated/magnetoluminesceable luminophore and its precursor are referred to as magnetically activated luminophores, which refer to chemical groups capable of undergoing a structural change after a magnetic reaction, thereby generating a luminescence phenomenon.
In the present invention, the luminophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable luminophore and a quencher, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to produce luminescence from the luminophore, which may be any suitable entity as described above that can produce luminescence upon excitation with light of a suitable wavelength.
It is noted that the same luminophore can exist simultaneously with one or more activated luminescence processes, such as dioxetane luminescence, oxalate peroxide luminescence, fluorescein luminescence, both chemically activated luminescence and biologically activated luminescence.
In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated. Groups that can act as pre-existing quencher energy acceptors include, but are not limited to: quenching dyes having a basic skeleton such as NPI, NBD, DABCYL, BHQ, ATTO, Eclipse, MGB, QXL, QSY, Cy, Lowa Black, and IRDYE, and quenching dye derivatives thereof include, specifically, the following:
Figure BDA0001936065950002112
Figure BDA0001936065950002121
ATT0540Q (trade name), ATT0580Q (trade name), ATT0612Q (trade name), Eclipse (trade name), MGB (trade name), QXL490 (trade name), QXL520 (trade name), QXL570 (trade name), QXL610 (trade name), QXL670 (trade name), QXL680 (trade name), Cy5Q (trade name), Cy7Q (trade name), Lowa Black FQ (trade name), Lowa Black RQ (trade name), IRDYE QC-1 (trade name).
In the present invention, the fluorophore having an aggregate fluorescence quenching property includes, but is not limited to, triphenylamine-based fluorophore, fused ring-based fluorophore, rylimide-based fluorophore, rubrene-based fluorophore, porphyrin-based fluorophore, phthalocyanine-based fluorophore, and the like, and specifically, the following may be cited:
Figure BDA0001936065950002122
in the invention, the quenching group can also be selected from a structure with fluorescence quenching performance generated by activating a part of force-sensitive elements/force-sensitive groups with force-sensitive characteristics under other actions besides the mechanical force action.
In the present invention, suitable activatable fluorophores, luminophores, quenchers, which may have two or more activation methods, may be used independently, simultaneously or sequentially, and the different activation methods may even produce different activation effects.
In the present invention, the force-sensitive moiety/group having force-sensitive property capable of generating a fluorophore and/or a quencher by an activation action of one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc. other than mechanical force is mainly selected from a radical type structure, a five-membered ring structure, a six-membered ring structure, a cyclobutane structure, a monoacyclocyclobutane structure, a dioxetane structure, a cyclobutene structure, a DA structure, a hetero DA structure, a light-operated DA structure, a [4+4] cycloaddition structure, a metal-ligand structure. The force-sensitive element/group with force-sensitive property capable of generating a luminophore by other than mechanical force, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc., is selected from dioxetane structures. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.
In the present invention, in order to obtain the desired force-responsive properties, the non-covalent single force-sensitive groups of the energy transfer-based composition must be aligned in a suitable manner, preferably with nearly parallel transfer dipole orientation, in addition to satisfying the partial overlap of the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor and the need for sufficient proximity of the energy donor and the energy acceptor.
The composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and comprises but is not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-component composite structure formed by multi-component combination of the tying, gating, parallel and serial structures and the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
In the present invention, the tethered complex force-sensitive moiety is formed by any suitable one of the above-mentioned covalent or non-covalent force-sensitive moiety/single force-sensitive moiety modules being bound to any suitable linker or linkers, wherein the force-sensitive moiety/single force-sensitive moiety module is tethered by the linker, and after the force-sensitive moiety/single force-sensitive moiety is activated, the tethered linker can prevent (at least temporarily) the polymer chain from chain scission due to chain scission caused by the activation of the chain scission type force-sensitive moiety/single force-sensitive moiety or the activated non-chain scission type force-sensitive moiety/single force-sensitive moiety from continuing to be stressed to cause chain scission. The complex force sensitive groups of the tethered structure are particularly useful for preventing, at least temporarily, or slowing down the chain scission of the polymer chains due to activation of the force sensitive groups, which is extremely important for both achieving force-responsive responsiveness and protecting the polymer from chain scission damage. A typical tethering force sensitive moiety has the general structural formula shown below, but the invention is not limited thereto.
Figure BDA0001936065950002131
Wherein the content of the first and second substances,
Figure BDA0001936065950002132
is force sensitive element/single force sensitive group;
Figure BDA0001936065950002133
is a linker, which may be selected from small molecule and large molecule linkers;
Figure BDA0001936065950002134
is a link to any suitable polymer chain/group/atom.
In the present invention, the tethering linker may be formed by at least one of a common covalent bond, a dynamic covalent bond, and a supramolecular interaction. The force-sensitive module can be composed of chain-breaking type covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, chain-breaking type non-dynamic covalent force-sensitive element/single force-sensitive group, chain-breaking type non-covalent force-sensitive element/single force-sensitive group. When the force-sensitive module is a chain-breaking non-dynamic covalent force-sensitive element/single force-sensitive group and the tethered connecting group is formed by common covalent bonds, the tethered structure is a non-dynamic non-chain-breaking tethered composite force-sensitive group. When only the force-sensitive module has dynamic covalent or non-covalent characteristics, and the tethered linker is formed by a common covalent bond, the tethered structure is a dynamic non-delinking tethered complex force-sensitive group. When the force-sensitive module has dynamic covalent character or non-covalent character and the tethering connection group is formed by dynamic covalent bond and/or supermolecular action, the tethering structure is a dynamic chain-breaking tethering composite force-sensitive group. When the force-sensitive module is a delinking non-dynamic covalent force-sensitive motif/single force-sensitive group and the tethered linker is formed by dynamic covalent bonds and/or supramolecular interactions, the tethered structure is a partially dynamic delinking tethered complex force-sensitive group. When the tethered linker is formed by only ordinary covalent bonds, the tethered linker is the most stable in structure and is most able to withstand complete chain scission of the polymer chain following activation by the tethered force-sensitive moiety/single force-sensitive group. Regardless of whether the force-sensitive module is dynamic or not, once the tethering linker contains dynamic covalent bonds and/or supramolecular interactions, the performance of the dynamic covalent bonds and/or supramolecular interactions can be realized by the dynamic covalent bonds and/or supramolecular interactions after final activation, and the force-sensitive module is dynamic.
In embodiments of the invention, the tethered complex force-sensitive groups preferably tether split homolytic, heterolytic, retrocyclic and non-covalent force-sensitive moieties/single force-sensitive groups of the split-chain type.
In an embodiment of the invention, the homolytic force sensing element/single force sensing group used for tethering is preferably a reversible free radical structure in the bis/polysulfide series, bis/polyselenium series, bis-aryl furanone series, bis-aryl cyclic ketone series, bis-aryl cyclopentenone series, bis-aryl chromene series, aryl biimidazole series, aryl ethane series, dicyano tetraaryl ethane series, aryl pinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane substituted ethane series, bifluorene series, allyl sulfide series, thio/seleno ester series.
In embodiments of the invention, the heterolytic mechanism force sensitive element/single force sensitive group used for tethering is preferably a structure in the triarylsulfonium salt series.
In an embodiment of the invention, the reverse cyclization mechanism force-sensitive moiety/single force-sensitive group used for tethering is preferably a structure in the cyclobutane series, dioxetane series, DA series, heteroda series, [4+4] cycloaddition series.
In an embodiment of the invention, the non-covalent force-sensitive motif/single force-sensitive group used for tethering is preferably a platinum alkyne ligand, an azacarbene with silver/copper/gold/ruthenium ligand, a boron nitrogen ligand, a palladium phosphorus ligand, a ruthenium ligand, a ferrocene, a cobaltocene.
In the embodiment of the present invention, the linking group for tethering is preferably a hydrocarbon group, a hydrocarbon group containing a heteroatom, a polyester group, a polyethylene glycol group.
In the embodiment of the present invention, some preferred tethered complex force-sensitive groups have the following general structural formula, but the present invention is not limited thereto.
Figure BDA0001936065950002135
Wherein the content of the first and second substances,
Figure BDA0001936065950002136
selected from:
Figure BDA0001936065950002137
wherein the content of the first and second substances,
Figure BDA0001936065950002138
selected from:
Figure BDA0001936065950002139
Figure BDA0001936065950002141
wherein the content of the first and second substances,
Figure BDA0001936065950002142
to be connected with n
Figure BDA0001936065950002143
An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, a fused ring structure, a bridged ring structure, and a nested ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphine atoms, and silicon atoms, and the hydrogen atoms bonded to the ring-forming atoms are arbitrarily and suitably selectedSubstituted or unsubstituted by an atom or substituent; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions
Figure BDA0001936065950002144
Are the same or different; unless otherwise indicated, appear hereinafter
Figure BDA0001936065950002145
The same meanings are given, and description thereof will not be repeated; wherein the content of the first and second substances,
Figure BDA0001936065950002146
is a link to any suitable polymer chain/group/atom;
Figure BDA0001936065950002147
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n is
Figure BDA0001936065950002148
The number of the cells.
In the embodiments of the present invention, some preferred tethered complex force-sensitive groups are exemplified below, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0001936065950002149
Figure BDA0001936065950002151
Figure BDA0001936065950002161
Wherein the content of the first and second substances,
Figure BDA0001936065950002162
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is selected from the group consisting of, but not limited to, a hydrogen atom, a hydrocarbon group.
In the present invention, the gated complex force sensitive moiety, which is formed by binding any suitable two or more covalent or non-covalent force sensitive motif/single force sensitive moiety modules, can be sequentially activated, and only the module which is used as a substrate can be activated after the module which is used as the gated module is activated. In gated complex force sensors with only two modules combined, one module is gated and the other is gated as substrate. In a gated complex force sensor comprising three modules, one of the modules is gated by both a preceding and a subsequent activation module. When four or more modules are contained in the gated complex force-sensitive cluster, and n represents the total number of modules, the number of modules which are both substrates of the preceding activation module and gated of the subsequent activation module is n-2. When the activation force of the gate control module is higher than that of the substrate module, once the gate control module is activated by force, the substrate module is immediately activated, on one hand, the gate control module protects the substrate module, on the other hand, the gate control module indirectly improves the activation force of the substrate module, the substrate module is favorable for the substrate module to play a role under the action of higher external force on a polymer, and the functional significance of stress warning and the like is particularly outstanding. When the activation force of the gating module is lower than that of the substrate module, the substrate is not activated immediately after gating activation, and the substrate must be activated after the external force rises to reach the threshold of the activation force; on one hand, sequential force-induced responses can be obtained through stepwise activation, and different responses can give different effects, such as stress warning and the like; on the other hand, when a polymer chain contains a plurality of the gated complex force-sensitive groups, activation of the substrate is started only after activation of all the activatable gates, so that stepwise multiple activation is generated, which is beneficial to protect the polymer and improve the toughness of the polymer in multiple layers besides sequential force-induced response. When the activation force of the gating module is equal to that of the substrate module, the substrate is rapidly activated after gating activation, although gating cannot effectively protect the substrate and cannot generate step-type activation, sequential activation of a plurality of modules can generate multiple identical or different force-induced responses, and the method also has a positive effect on improving the toughness of the polymer. A typical gated complex force-sensitive moiety has a general structural formula as shown in the following formula, but the present invention is not limited thereto.
Figure BDA0001936065950002171
Wherein the content of the first and second substances,
Figure BDA0001936065950002172
is a force sensitive element/single force sensitive group, and p is the number of modules which are not only substrates of a preceding activation module but also gates of a following activation module;
Figure BDA0001936065950002173
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different;
Figure BDA0001936065950002174
is a link to any suitable polymer chain/group/atom.
In the present invention, the gating module may be selected from the group consisting of a chain-broken type and a non-chain-broken type. The substrate module may also be of the delicatessen or non-delicatessen type. Regardless of whether the gating module and the substrate module are of the broken-chain type, it must be ensured that the gating module is activated prior to the substrate module being subjected to force. The chain-breaking gating module comprises chain-breaking covalent force-sensitive elements/single force-sensitive groups with dynamic covalent characteristics, chain-breaking non-dynamic covalent force-sensitive elements/single force-sensitive groups and chain-breaking non-covalent force-sensitive elements/single force-sensitive groups. When the gating module and the substrate module are both selected from any one of a chain-breaking covalent force-sensitive element/single force-sensitive group and a chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the gating composite force-sensitive group has complete dynamic; however, if only one module is selected from any one of the chain-breaking covalent force-sensitive element/single force-sensitive group and the chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent character, the gated composite force-sensitive group has only partial dynamic property.
In the present invention, the linking group in the gated composite force sensitive group can be selected from small molecule or large molecule linking groups formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein the linker formed by the common covalent bond facilitates force activation of the substrate module. A linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.
In an embodiment of the present invention, the preferred gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain-breaking type, including but not limited to homolytic, heterolytic, reverse cyclic, and non-covalent force-sensitive element/single force-sensitive group; the substrate force-sensitive moiety/monodispersion may be any suitable force-sensitive moiety/monodispersion, preferably homolytic, heterolytic, reverse cyclization, electrocyclization, bending activation and non-covalent force-sensitive moiety/monodispersion.
In embodiments of the present invention, preferred gating moieties/groups include, but are not limited to, disulfide bonds, diselenide bonds, diarylfuranone groups, diarylcycloketo groups, diarylcyclopentenedione groups, diarylchromone groups, arylbiimidazolyl groups, arylethyl groups, dicyanotetraarylethyl groups, arylpinacol groups, alkoxyamino groups, alkylthioamino groups, cyclohexadienone groups, tetracyanoethyl groups, cyanoacylethyl groups, adamantane-substituted ethyl groups, dibenzoenyl groups, allylthioether groups, thioester groups, selenoate groups, cyclobutane groups, dioxethyl groups, DA cyclic groups, hetero DA cyclic groups, [4+4] cyclic groups, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocene, cobaltocene.
In embodiments of the present invention, preferred substrate motifs/groups include, but are not limited to, disulfide bonds, bisseleno bonds, bisarylfuranones, bisarylcycloketones, bisarylcyclopentenediones, bisarylene-based, arylbiimidazoles, arylethanes, dicyanotetraarylethanes, arylpinacols, alkoxyamines, alkylthioamines, cyclohexadienones, tetracyanoethanes, cyanoacylethanes, adamantane-substituted ethanes, bifluorenes, allylthioether groups, thioesters, selenoates, cyclobutanes, dioxetanes, DA cyclics, hetero DA cyclics, [4+4] cyclics, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocenes, cobaltocenes, six-membered rings, five-membered rings, Cyclopropane, oxirane.
Some preferred gated complex force sensors are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0001936065950002181
Wherein the content of the first and second substances,
Figure BDA0001936065950002182
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r1Is hydrogen, hydroxy, a protecting group, R2Is hydrogen, halogen, R3Hydrogen, a fluorophore.
In the present invention, a parallel composite force-sensitive cluster is formed by combining any suitable two or more suitable force-sensitive elementary/single force-sensitive cluster modules in a parallel connection manner, wherein all the force-sensitive elementary/single force-sensitive cluster modules can be stressed simultaneously. Wherein, the parallel force-sensitive elements/single force-sensitive mass modules can be the same or different; when the same, the activation force required by one parallel complex force-sensitive cluster is equivalent to the activation force required by two or more single force-sensitive clusters, and each force-sensitive element/single force-sensitive cluster module will typically be activated simultaneously; when not identical, different force-sensitive elements/single force-sensitive mass modules may not activate simultaneously if the activation force is different for each force-sensitive mass. A typical parallel complex force-sensitive group has a general structural formula shown in the following formula, but the invention is not limited thereto.
Figure BDA0001936065950002183
Wherein the content of the first and second substances,
Figure BDA0001936065950002184
the force-sensitive elements/single force-sensitive groups are arranged, m is the number of the force-sensitive elements/single force-sensitive groups connected in parallel, and the force-sensitive elements/single force-sensitive groups at different positions can be the same or different; r, R,
Figure BDA0001936065950002185
The linking group can be selected from small molecule linking groups and large molecule linking groups, and the linking groups at different positions can be the same or different;
Figure BDA0001936065950002186
is a link to any suitable polymer chain/group/atom.
In the invention, the force-sensitive modules in the parallel composite force-sensitive clusters can be selected from a chain-breaking type and a non-chain-breaking type. When any one force sensitive module is in a dynamic chain-breaking structure, the dynamic property is conveniently provided. When all the parallel force-sensitive modules are selected from covalent force-sensitive group elements/single force-sensitive groups and non-covalent force-sensitive group elements/single force-sensitive groups with dynamic covalent characteristics, the parallel composite force-sensitive groups are dynamic chain-breaking composite force-sensitive groups. When any one force-sensitive module is a non-dynamic covalent force-sensitive element/single force-sensitive group and the connecting group is a common covalent bond structure, the parallel composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.
In the present invention, the linking group in the parallel composite force sensitive group can be selected from small molecule or large molecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein, the connecting base formed by common covalent bond is convenient for the force activation of the force sensitive module; a linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.
Some preferred parallel complex force-sensitive clusters are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0001936065950002191
Wherein the content of the first and second substances,
Figure BDA0001936065950002192
for attachment to any suitable polymer chain/group/atom, attachment to the polymer chain is preferably via an ether linkage, an ester group, a phenoxy group, an amide linkage, a urethane linkage, a tertiary amine group, a triazole group, a double bond. In the present invention, the activation force required by the parallel force sensing mass is the sum of the individual parallel units, but not the sum effect when the individual units are not activated simultaneously. The parallel force sensitive groups provide richer performance and selection for the force-induced response of the material, and particularly the comprehensive mechanical strength of the force sensitive groups can be improved.
In the invention, the tandem composite force-sensitive cluster is formed by combining any suitable two or more force-sensitive cells/single force-sensitive cluster modules in a tandem connection manner, the tandem connection group between any two adjacent force-sensitive cells/single force-sensitive cluster modules is part of any one of the two adjacent tandem force-sensitive cells/single force-sensitive cluster modules, and is an indispensable part for realizing force responsiveness/effect of any one of the tandem force-sensitive cells/single force-sensitive cluster modules, and each tandem force-sensitive cell/single force-sensitive cluster module can be activated under the action of a suitable mechanical force. A typical tandem complex force-sensitive group has a general structural formula shown in the following formula, but the present invention is not limited thereto.
Figure BDA0001936065950002193
Wherein the content of the first and second substances,
Figure BDA0001936065950002194
being force-sensitive elements/force-sensitive masses, force-sensitive elements in different positionsThe single force sensitive groups may be the same or different; r, L is a linker which may be selected from small molecule and large molecule linkers, the linkers at different positions may be the same or different; n and m are the number of the force sensitive elements/single force sensitive groups connected in series;
Figure BDA0001936065950002201
is a link to any suitable polymer chain/group/atom.
In the present invention, the force-sensitive modules in the series-connected composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the tandem composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the series-connection composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.
In the invention, the linking group in the tandem composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.
In the embodiment of the invention, the force sensitive element/single force sensitive group in the series composite force sensitive group is a non-chain-breaking module, preferably formed by combining a six-membered ring unit and a five-membered ring unit. Some preferred tandem composite force-sensitive groups are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0001936065950002202
Figure BDA0001936065950002211
Wherein the content of the first and second substances,
Figure BDA0001936065950002212
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r1、R2Are any suitable groups/atoms, preferably hydrocarbon groups and hydrogen atoms. The series composite force sensitive group based on the six-membered ring and the five-membered ring is particularly suitable for obtaining multi-level force-induced color change/fluorescence response, can induce different stress effects and obtain synergistic effect through multi-level color change and mixed color/fluorescence, and has important significance for obtaining multifunctional force-induced response.
In the present invention, any one or more of the tethered, gated, parallel, and tandem modules can also be recombined with any suitable one or more force-sensitive motifs and/or single force-sensitive groups and/or linker modules, or any suitable two or more of the tethered, gated, parallel, and tandem modules, to obtain a multiplex composite force-sensitive group. For example, a gated multi-element force sensor group is obtained by tethering a gated composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the tethered composite force sensor group and a single force sensor group module, a multi-level gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the single force sensor group module, two or more series composite force sensor groups are combined into a parallel multi-element composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the series composite force sensor group and the tethered composite force sensor group, a gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the series composite force sensor group, a series multi-element force sensor group is obtained by combining the parallel composite force sensor group and the series composite force sensor group, and a multi-element force sensor group is obtained by continuously tethering the series multi-element force sensor group, and the like. The technical personnel in the field can carry out reasonable combination according to the guidance of the invention to prepare the multielement composite force sensitive groups with various structures and excellent performance. Some exemplary multi-element force-sensitive compound structures are shown below, but the invention is not limited thereto.
Figure BDA0001936065950002221
Wherein the content of the first and second substances,
Figure BDA0001936065950002222
the force-sensitive elements/single force-sensitive groups at different positions can be the same or different;
Figure BDA0001936065950002223
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n, m and q are the number of the force sensitive elements/single force sensitive groups/compound force sensitive groups/multi-element compound force sensitive groups connected in series/in parallel, and p is the number of gated modules which are not only substrates of the preceding activation modules but also the subsequent activation modules;
Figure BDA0001936065950002224
is a link to any suitable polymer chain/group/atom.
In the present invention, the force-sensitive modules in the multicomponent composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the multi-element composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the multi-element composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group which has certain dynamic property and is convenient to provide the dynamic property.
In the invention, the linking group in the multi-element composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.
In the invention, the dynamic chain-breaking type multi-component composite force sensitive group must meet the characteristics of dynamic and chain-breaking, and the non-dynamic chain-breaking type multi-component composite force sensitive group only needs to not meet one of the characteristics of dynamic or chain-breaking.
In the embodiment of the present invention, in the multi-element composite force-sensitive group, preferably, the tethered composite force-sensitive element/single force-sensitive group is of a chain-broken type, including but not limited to homolytic, heterolytic, and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain breaking type, including but not limited to homolytic, heterolytic and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the force-sensitive element/single force-sensitive group in the series-connection composite force-sensitive group is a non-chain-breaking module. Some preferred multi-element force-sensitive compounds are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0001936065950002231
Figure BDA0001936065950002241
Wherein the content of the first and second substances,
Figure BDA0001936065950002242
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is any suitable group/atom, preferably a hydrocarbyl group, a methoxy group and an ester group; r1Is hydrogen, hydroxy, a protecting group, R2Is hydrogen, halogen, R3Hydrogen, a fluorophore. The multi-element composite force-sensitive group is beneficial to obtaining multi-level/multiple responses through one force-sensitive group by fusing multi-element/multi-level composite/single force-sensitive group/force-sensitive elements, and maximally utilizes the force-induced response effect.
In the present invention, typical covalent single force sensitive groups with dynamic covalent character include, but are not limited to: the disulfo/polysulfide series, the diseleno/polyselene series, the diarylfuranone series, the diarylcycloketone series, the diarylcyclopentenedione series, the diarylchromene series, the arylbiimidazole series, the arylethane series, the dicyanotetraylethane series, the arylpinacol series, the chain transfer series, the cyclohexadienone series, the tetracyanoethane series, the cyanoacylethane series, the bifluorene series, the allylthioether series, the thio/selenoate series, the cyclobutane series, the monocyclobutane series, the diazocyclobutane series, the DA series, the hetero DA series, the light-operated DA series, the [4+4] cycloaddition series, the covalent monoensitive group. The covalent single force sensitive group with the dynamic covalent characteristic has reversible force-activated characteristic, namely, after the force sensitive group is subjected to force activation, the force sensitive group can be reformed through reversible fragmentation, exchange or recombination and the like, so that the force-responsive polymer can be endowed with the recyclable/repeatable force-activated characteristic and the self-repairing and/or self-reinforcing performance.
In the present invention, typical non-delinking covalent single force sensitive groups include, but are not limited to: triaryl sulfonium salt series, six-membered ring series, five-membered ring series and three-membered ring series covalent single force sensitive groups. The non-chain-breaking covalent single-force sensitive group does not cause polymer chain breakage in the process of force activation, can well maintain the structural stability of the polymer, and avoids the reduction of covalent crosslinking degree, mechanical strength and modulus caused by force activation.
In the present invention, typical covalent single force sensitive groups of the delinking type non-dynamic covalent character include, but are not limited to: peroxide series, azonitrile series, o-phthalaldehyde series, sulfonic group series, dioxetane series and double nitrite series. The chain-breaking type covalent single force sensitive group with the non-dynamic covalent characteristic can cause the breakage of a polymer chain in the force activation process, so that the force degradation effect is convenient to obtain, and in the force response process, the total crosslinking degree of the polymer is reduced, so that the acceleration of the activation of other force sensitive groups contained in the polymer is facilitated.
The non-covalent single force sensitive groups described in the present invention are formed by non-covalent interactions, have non-covalent dynamics that confer reversible force-activation properties to the non-covalent single force sensitive groups, and exhibit cyclable/reproducible force-activation characteristics.
In the present invention, when the force-sensitive group also has the property of a dynamic covalent bond, the force-sensitive group is not considered to be either a non-dynamic covalent bond or a normal dynamic covalent bond, unless otherwise specified. As used herein, unless otherwise specified, a non-covalent force-sensitive group is considered only to be a force-sensitive group, and when present, a non-covalent interaction refers specifically to non-covalent interactions other than non-covalent force-sensitive groups.
In the invention, the bond energy of common covalent bond is higher, and has no selectivity to mechanical force, and the common covalent bond can be sensed only when the structure is greatly damaged or completely destroyed, while the bond energy/fracture energy of the covalent force sensitive group is relatively lower, and the covalent force sensitive group has selective preferential fracture, elimination, bonding, isomerization and other chemical changes to force, and can obtain specific force-induced responsiveness; the non-covalent force sensitive groups in the force-induced responsive polymer are used as a type of force sensitive groups formed based on non-covalent action, and under the action of force, the non-covalent force sensitive groups can be dissociated and recombined, such as the dissociation of the non-covalent force sensitive groups based on coordination bonds, the disassembly of supramolecular assemblies, the separation of compositions, the separation of aggregates and other physical changes, so that specific force-induced response is obtained. The force sensitive groups change specific chemical and/or physical signals and generate new groups/new substances and the like after being activated by force, so that effective detection, monitoring and warning effects are provided for the processes of stress, deformation, structural damage and failure of the polymer, information such as the stress position and size of the material is fed back in real time, and prevention and optimization are facilitated.
In the invention, the stress induction and damage warning can be directly carried out except for mechanochromism, mechanochromatism/phosphorescence change, mechanoluminescence and the like, and the invention also has the functions of ion release, mechanocatalysis, polymerization initiated by a force-induced free radical, force-induced self-repair, force-induced crosslinking, force-induced grafting and the like. For example, when a force-sensitive element/single force-sensitive group with dynamic covalent characteristics and/or non-covalent action is used, the force-sensitive element/single force-sensitive group has certain self-repairing performance after being activated by force, can also have the functions or effects of shape memory, plasticity, formation of new cross-linking and the like, and has abundant performance and application; after force activation, the force sensitive group containing the spirothiopyran structure can react with a reactive group contained on a polymer or a reactive group generated by a precursor of the spirothiopyran structure under a specific condition, such as maleimide or a precursor of the spirothiopyran structure, such as a DA structure which can be pyrolyzed and/or activated by force, and the like, so that the spirothiopyran structure has functions of functionalization, force-induced self-repair, force-induced crosslinking/enhancement and the like; the specific structure of the force sensitive element/single force sensitive group through the homolytic mechanism can initiate free radical polymerization or crosslinking after being activated, thereby changing the structure of a polymer system; the supermolecular complex structure, particularly a coordination structure, can be activated to generate a catalyst, catalyze reactions such as organic reaction, polymerization or crosslinking, enhance luminescence and fluorescence, provide self-repairing effect, generate force-induced crosslinking and the like, for example, force-induced generation of Grubb's catalyst, and catalyze olefin metathesis reaction to generate polymerization or crosslinking; after force-induced activation, force-sensitive groups of various cyclobutane structures can generate photoinduced ring closing reaction, free radical polymerization/crosslinking reaction, click chemical reaction and the like, so that the functions of self-repairing, force-induced enhancement and the like are achieved; the specific force sensitive group containing epoxy group structure is activated to generate a ylide structure, and then reacts with cyano group to be functionalized, grafted or crosslinked, so as to achieve the effect of modification or crosslinking. The properties obtainable by the present invention are far more than these, and the properties obtainable are well understood by the skilled person on the basis of the force sensitive groups and polymer structures proposed by the present invention.
In the invention, the force-responsive polymer contains at least two force-sensitive groups, and two or more force-sensitive groups can be reasonably designed and combined according to requirements to obtain force responsiveness/effects of diversity, cooperativity, orthogonality and/or orderliness and the like; different force sensitive groups with different elementary structures are preferably used so as to better perform performance regulation and meet various requirements on force-induced response performance and use to the maximum extent. Wherein, the orthogonality refers to that the force activation processes among the multiple force sensitive groups do not influence each other; the synergy means that the force activation process of one or more of the different force sensitive groups triggers/promotes the force activation process of other force sensitive groups and produces larger effect than the linear superposition of respective force responsiveness; the sequentiality refers to the difference of force activation magnitude and action form among different force sensitive groups, positions of the force sensitive groups in a cross-linked network, cross-linking degree and the like, and the sequential force response is shown under different force actions. In the invention, by selecting different suitable force-sensitive groups, the mutual reaction between different force-sensitive group activation products can be obtained, and the effects of in-network and/or inter-network reaction and the like can be achieved. In the invention, the functions of gating, mutual induction and the like among networks can be achieved through different network structures, different positions of the force sensitive groups, different selections of the force sensitive groups and the like.
In the present invention, by combining the use of force sensitive groups of different force activation mechanisms, a richer force-induced response performance/effect can be obtained, preferably the following force sensitive group combinations: the preparation method comprises the following steps of (1) at least two covalent force sensitive groups based on a homolytic mechanism, wherein the force sensitive groups have obvious force responsiveness, including but not limited to color change, free radical polymerization initiation, oxidation resistance and conductivity improvement, and are convenient to prepare polymers with rich and adjustable force responsiveness; the covalent force sensitive groups are chain-broken covalent force sensitive groups, any one force sensitive group can cause the reduction of covalent crosslinking degree after force-induced activation, the polymer network structure is changed while the force-induced responsiveness is obtained, and the sequential force-induced activation process and the mutual reaction between activated products can be obtained by selecting the proper force sensitive groups from different groups, so that the synergistic force-induced response effect is obtained; the covalent force sensitive group based on the homolytic mechanism and the covalent force sensitive group based on the electrocyclization mechanism are respectively a chain-breaking type covalent force sensitive group and a non-chain-breaking type covalent force sensitive group, and sequential and multiple force-induced color-changing effects can be more easily obtained through respective activation signal differences; the covalent force sensitive group based on the reverse cyclization mechanism and the covalent force sensitive group based on the electrocyclization mechanism, wherein the covalent force sensitive group is a chain-breaking type covalent force sensitive group, the force-activated product of the covalent force sensitive group has rich reactivity and is convenient to carry out force-induced crosslinking, the covalent force sensitive group is a non-chain-breaking type covalent force sensitive group, the force-activated product of the covalent force sensitive group has rich property changes such as color, spectral absorption, fluorescence emission and the like and has good reactivity, and the polymer has a better mechanical force induction function and is easy to obtain an orthogonal and/or synergistic force-activated effect by combining the force sensitive groups; two covalent force sensitive groups based on a reverse cyclization mechanism can prepare force-induced responsive polymers with abundant color change and luminescence property based on the abundant change of the properties of force sensitive groups such as mechanochromism, mechanocuminescence and the like; the two covalent force sensitive groups based on an electrocyclic mechanism are combined to use, so that a polymer with abundant force-induced discoloration performance can be conveniently prepared, abundant active groups can be generated, force-induced crosslinking and force-induced enhancement are facilitated, and after the force sensitive groups are completely activated, the crosslinking structure of the force sensitive groups cannot be damaged, namely, the polymer chain breakage cannot be caused, and the structural stability and the mechanical strength of the polymer can be favorably maintained; the force sensitive groups are used in combination, so that the polymer with abundant force-induced color change and force-induced fluorescence/phosphorescence change can be conveniently prepared, and the stress and deformation of the material can be conveniently and visually sensed; the polymer with integrated multiple responsibilities such as strongly-induced catalysis, strongly-induced fluorescence, strongly-induced enhancement, strongly-induced toughening, strongly-induced discoloration and the like is conveniently prepared by mixing the covalent force sensitive groups and the non-covalent force sensitive groups, so that the performance of the polymer is more diversified.
In the present invention, in addition to the non-covalent force-sensitive groups based on energy transfer compositions described above, specific force-sensitive groups, as well as polymer structure and force activation, can also result in force-induced energy transfer. The term "energy transfer" as used herein also refers to the transfer of photon energy from an energy donor to an energy acceptor. However, at least one of the energy donor and the energy acceptor must be generated directly and/or indirectly by force-induced activation. Thus, it can be considered as an "indirect" energy transfer by force, where activation by force directly and/or indirectly produces an energy donor and/or acceptor, followed by energy transfer.
In the present invention, the combination of the energy donor and the energy acceptor that generates the force-induced energy transfer may include, but is not limited to, the following cases: the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated directly by force and the energy acceptor generated directly by force, the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated indirectly by force and the energy acceptor generated directly by force, the energy donor generated indirectly by other non-force and the energy acceptor generated directly by force, and the energy donor generated indirectly by force and the energy acceptor generated indirectly by force. Furthermore, the present invention does not exclude that activation of a suitable force sensitive moiety under suitable conditions may generate both an energy donor or an energy acceptor, directly and indirectly, or both. Moreover, when multiple energy donors and multiple energy acceptors are contained in the same polymer, more than one source of each energy donor and energy acceptor may be present. Wherein said other non-force-inducing source means that said energy donor/energy acceptor may be directly and/or indirectly generated in addition to said force-inducing activation, including but not limited to pre-existing, photo-activated, thermo-activated, electro-activated, chemically activated, bio-activated, magnetically activated.
Furthermore, in embodiments of the present invention, in addition to force-induced energy transfer, other forms of energy transfer may occur in the polymer, i.e., energy transfer between energy donors of other non-force-induced sources and energy acceptors of other sources. In embodiments of the present invention, in addition to the fact that the energy donor and energy acceptor generated directly by force activation of the force sensitive moiety must be on the polymer chain, the energy donor and energy acceptor generated indirectly by force activation of the force sensitive moiety and other non-force-causing sources may or may not be on the polymer chain, preferably on the polymer chain; preferably, the distance between the energy donor and the energy acceptor is not more than 10nm, more preferably on the same polymer chain, even more preferably on the same polymer chain and the distance is not more than 10 nm. In the invention, the energy transfer including energy transfer caused by force can be organically regulated and controlled by designing, selecting and adjusting the type, the quantity, the combination and the like of the energy donor/energy donor from other non-force-caused sources, so that excellent and diversified energy transfer performance and wide application can be obtained.
In the present invention, the energy donor and the energy acceptor in the energy transfer may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.
In the present invention, the energy transfer may be only one stage or may be multi-stage. When the energy transfer polymer contains a plurality of fluorophores/luminophores (precursors), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is used as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, thereby realizing the phenomenon of multi-stage energy transfer. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.
In the present invention, the fluorophore may be selected from the group consisting of, but not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates, and combinations thereof. The fluorophore may be selected from, but not limited to, pre-existing, chemically activated, biologically activated, photo-activated, thermally activated, electro-activated, and magnetically activated, in addition to being force-activated. In embodiments of the present invention, the pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive generated, magnetically activated generated fluorophores are identical to the fluorophores of the non-covalent force-sensitive groups based on energy transfer compositions described above and will not be described herein.
In the present invention, the force-activated fluorophore refers to a fluorescent entity whose excitation wavelength and/or emission wavelength of fluorescence generated by the precursor changes its structure under the action of mechanical force, and the precursor may be referred to as a fluorescence force-sensitive group. The fluorescent force sensitive moiety may or may not fluoresce prior to force activation, but may fluoresce after activation. Wherein, the fluorescence force-sensitive group contains force-sensitive elements, and the force-sensitive elements include but are not limited to covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions and aggregates.
In the invention, the fluorescence force sensitive groups comprise fluorescence single force sensitive groups and fluorescence composite force sensitive groups. Wherein the fluorescent single force sensitive group comprises only one force sensitive moiety or only one force sensitive moiety in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-induced response signal, comprising a covalent fluorescent single force sensitive group and a non-covalent fluorescent single force sensitive group. Wherein, the fluorescence composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent fluorescence force-sensitive elements/single force-sensitive groups (including combining with non-fluorescence force-sensitive elements/single force-sensitive groups), and the fluorescence composite force-sensitive group comprises but not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-composite structure formed by multi-stage combination of the two or more of the tying, gating, parallel and serial structures and the fluorescence and/or non-fluorescence force-sensitive elements/single force-sensitive groups. The fluorescent complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
In the invention, the covalent fluorescence force-sensitive element mainly relates to chemical changes such as breaking, elimination, bonding and isomerization of covalent bonds under the action of mechanical force, including but not limited to homolytic cleavage, reverse cyclization, electrocyclic ring opening, bending activation and isomerization; the non-covalent fluorescence force sensitive element mainly relates to physical changes such as dissociation of a supramolecular complex, disassembly and assembly of an assembly body, separation of a composition, separation of an aggregate and the like under the action of mechanical force. In the embodiment of the present invention, the fluorescence force-sensitive element or the force-sensitive group is as described in the foregoing, and thus, the description thereof is omitted here. It is noted that the non-covalent fluorescent force-sensitive groups based on the composition include non-covalent fluorescent force-sensitive groups based on an energy transfer composition.
In the present invention, the luminophore in the energy transfer may be generated by force activation, and may be selected from, but not limited to, chemical activation, photoactivation/photoluminescence, thermal activation/thermoluminescence, electrical activation/electroluminescence, magnetic activation/photoluminescence. In embodiments of the present invention, the pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive generated, magnetically activated generated luminophores are the same as those of the non-covalent force sensitive groups based on energy transfer compositions described above and are not described herein.
In the present invention, the solid structure capable of being force-activated to generate luminophores is called luminous force sensitive group, which refers to a force sensitive group capable of generating a luminous phenomenon by a structural change under the action of stress, and includes, but is not limited to, a dioxetane-based luminous single force sensitive group and a composite force sensitive group. In the embodiment of the present invention, the luminescent force-sensitive element or the force-sensitive cluster is as described in the foregoing, and will not be described herein.
In the present invention, said quencher in the energy transfer is also as described for the non-covalent force-sensitive group based energy transfer composition and is not described herein in detail.
In the present invention, a moiety capable of acting as a force-sensitive moiety/group can also be capable of generating a fluorophore and/or a luminophore and/or a quencher by other actions than mechanical forces, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, and the like. Force-sensitive moieties/groups with force-sensitive properties capable of generating fluorophores and/or quenchers by other actions than mechanical forces, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc., are selected from the group consisting essentially of free radical type structures, five-membered spirocyclic structures, six-membered spirocyclic structures, five-membered ring structures, six-membered ring structures, cyclobutane structures, monoazetidine structures, dioxetane structures, cyclobutene structures, DA structures, hetero DA structures, light-controlled DA structures, [4+4] cycloaddition structures, metal-ligand structures. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.
In the present invention, when the energy donor and the energy acceptor are indirectly generated by the force-induced activation of the force-sensitive group, the activation of the force-sensitive group may result in the generation of the energy donor and/or the energy acceptor by other structures, or the activation of the force-sensitive group may result in the regeneration of the activation product thereof into the energy donor and/or the energy acceptor by other actions. For example, a carbene-metal ligand non-covalent force sensitive group is contained in a polymer cross-linked network, and after the carbene-metal ligand non-covalent force sensitive group is activated by mechanical force, the generated carbene can react with dioxetane to enable the dioxetane to emit light and become an energy donor; for another example, a carbene-copper ligand non-covalent force sensitive group is contained in a polymer cross-linked network, and after the carbene-copper ligand non-covalent force sensitive group is activated by mechanical force, the generated copper can catalyze azido coumarin to react with phenylalkyne, and the generated strong fluorescent substance can be used as an energy receptor; for another example, the dioxetane compound connected with the cinnamic acid dimer is firstly activated by mechanical force to open the ring of the cyclobutane in the cinnamic acid dimer, then the dioxetane connected with the cinnamic acid is generated, the luminous intensity and the luminous wavelength of the dioxetane are changed, and then the alkaline substance is used for activating the dioxetane to open the ring and emit light, so that the dioxetane compound can be used as an energy donor.
In the present invention, suitable activatable fluorophores, luminophores, quenchers, which may have two or more activation methods, may be used independently, simultaneously or sequentially, and the different activation methods may even produce different activation effects.
In the present invention, it is also preferable to incorporate at least one force-sensitive element/single force-sensitive group capable of force-activating to directly generate a functional donor and/or acceptor into one composite force-sensitive group, and the corresponding energy acceptor and donor are also in the composite force-sensitive group structure; more preferably, both the energy acceptor and donor are generated by force-induced activation of the force sensitive moiety in the complex force sensitive moiety. Thus, through the force-induced activation of the composite force-sensitive groups, energy transfer can be generated in the activated composite force-sensitive groups, the efficiency is high, and different force-sensitive elements/single force-sensitive groups in the composite force-sensitive groups can be repeatedly utilized.
In the present invention, the force-sensitive groups contained in the force-responsive polymer are optionally present in a side chain backbone in addition to the crosslinked polymer network backbone. In the present invention, it is also not excluded that the force-sensitive groups may be located in side groups and end groups of the polymer chain, but for covalent force-sensitive groups, since no force is applied in side groups and end groups, they do not achieve a force-induced response. However, force sensitive moieties of the present invention that are not force activated may also facilitate suitable reactions and/or responses under other suitable conditions. The number of the force-sensitive groups between any two crosslinking points and the ratio thereof to all the bonds are not particularly limited, and may be one or more, preferably contain only one.
The supramolecular action described in the present invention includes, but is not limited to, at least one of the following: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding interaction, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding interaction, radical cation dimerization. Supramolecular interactions are non-covalent, which also includes phase separation and crystallization. In the present invention, non-covalent/supramolecular interactions are only considered to be non-covalent/supramolecular interactions unless specifically stated otherwise.
In the present invention, the non-covalent interaction may be a weak dynamic non-covalent interaction that does not dissociate/break during the normal use of the force-responsive polymer, which generally cannot undergo dynamic dissociation and generate interconversion dynamic behavior at the material working temperature and without applying external field action, etc.; or a non-covalent action with strong dynamic property in the normal use process of the force-induced response polymer, which can generate dynamic behavior of dynamic dissociation and mutual conversion under the conditions of material working temperature, no external field action and the like; the working temperature of the material is generally not higher than 60 ℃ and preferably not higher than 25 ℃. In the polymer containing strong dynamic noncovalent action, the exchange speed of the noncovalent action is high, and monomers at different positions can be exchanged, so that the force sensitive groups can be activated to a greater extent, and the polymer which is activated more uniformly can be obtained more easily. Dissociation/fragmentation can also occur under certain conditions, such as weak dynamic non-covalent interactions under the action of high temperatures, strong competitive substances, strong mechanical forces, etc.
In the present invention, non-covalent interactions are, as not specifically stated, considered only as non-covalent interactions and not as force-sensitive moieties/groups; when the force-sensitive group also contains a group/unit that can form a noncovalent interaction and the group is one of the characteristic groups that constitute the force-sensitive group, the group/unit is considered only as part of the force-sensitive group and not solely as a noncovalent moiety, as is not specifically stated; if not specifically stated, what is considered to be a non-covalent interaction of a force-sensitive moiety/group is used only as the force-sensitive moiety/group.
The hydrogen bonding in the present invention refers to any suitable supramolecular interaction established by hydrogen bonding, which is generally linked by hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, with hydrogen as medium between Z and Y, to generate hydrogen bond in the form of Z-H … Y, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, which may be selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably from atoms of F, N, O, and more preferably from atoms of O, N. The hydrogen bond can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three.
In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.
Figure BDA0001936065950002281
The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:
Figure BDA0001936065950002282
in embodiments of the present invention, the greater the number of teeth in the hydrogen bond, the greater the synergistic effect, and the greater the strength of the hydrogen bond. 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 hydrogen bond can play a role in promoting the polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, and the dynamics of the hydrogen bonding action is strong. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.
In embodiments of the invention, the hydrogen bonding may be effected by the presence of non-covalent interactions between any suitable hydrogen bonding groups. Wherein, the hydrogen bond group can only contain a hydrogen bond donor, only contain a hydrogen bond acceptor, or contain both the hydrogen bond donor and the hydrogen bond acceptor, preferably contain both the hydrogen bond donor and the hydrogen bond acceptor. Wherein, the hydrogen bonding group preferably comprises the following structural components:
Figure BDA0001936065950002283
more preferably at least one of the following structural components:
Figure BDA0001936065950002291
further preferably at least one of the following structural components:
Figure BDA0001936065950002292
wherein the content of the first and second substances,
Figure BDA0001936065950002293
refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom.
In the embodiments of the present invention, the hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazolyl groups, imidazolyl groups, imidazolinyl groups, triazolyl groups, purine groups, porphyrin groups, derivatives thereof, and the like.
In the present invention, said hydrogen bonding groups may be present only on the polymer chain backbone (including side chains/branches/bifurcations), referred to as backbone hydrogen bonding groups; or may be present only in pendant groups (also including multilevel structures of pendant groups), referred to as pendant hydrogen bonding groups; or may be present only on the polymer chain/small molecule end group, referred to as an end hydrogen bonding group; or may be present in at least two of the polymer chain backbone, the polymer chain pendant group, the polymer chain/small molecule end group. When present on at least two of the polymer chain backbone, the polymer chain pendant groups, and the polymer chain/small molecule end groups at the same time, hydrogen bonds may be formed between hydrogen bonding groups in different positions, in particular instances, for example, the backbone hydrogen bonding groups may form hydrogen bonds with the pendant hydrogen bonding groups. The hydrogen bonding groups may also be present in polymer constituents such as small molecule compounds or fillers, referred to as other hydrogen bonding groups.
By way of example, the following backbone hydrogen bonding groups may be mentioned, but the invention is not limited thereto:
Figure BDA0001936065950002294
Figure BDA0001936065950002301
by way of example, the following pendant/terminal hydrogen bonding groups may be mentioned, without the invention being restricted thereto:
Figure BDA0001936065950002302
Figure BDA0001936065950002311
wherein x, m and n are the number of repeating units, and may be fixed values or average values, preferably less than 20, and more preferably less than 5.
Other hydrogen bonding groups in the present invention may be any suitable hydrogen bonding structure.
The hydrogen bonding action in the invention is various in types, including but not limited to the hydrogen bonding action of one or more of skeleton hydrogen bonding groups, side group hydrogen bonding groups, end group hydrogen bonding groups or other hydrogen bonding groups, and the hydrogen bonding action/crosslinking with the supramolecular action strength, supramolecular dynamics and supramolecular crosslinking density being widely adjustable is obtained. Different hydrogen bonding actions have respective structural differences and performance characteristics, for example, the hydrogen bonding action formed by the participation of the side group hydrogen bonding group and the end group hydrogen bonding group has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bonding density and the like, a quick self-repairing process is easily obtained, and the tear resistance can be better improved; and the skeleton hydrogen bond group is positioned on a skeleton chain, so that the mechanical strength and the structural stability are easier to promote, 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, the same polymer system may contain one or more than one hydrogen bonding group, and the same cross-linking network may also contain one or more than one hydrogen bonding group, that is, the polymer may contain a combination of one or more than one hydrogen bonding group. The hydrogen bonding groups may be formed by reaction between any suitable groups, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid 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 reaction between the succinimide group and amino, hydroxyl, sulfhydryl groups.
Among them, the metal-ligand interaction described in the present invention refers to a supramolecular 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, a coordinating atom or ion may form one or more coordination bonds with one or more metal centers, and a metal center may also form one or more coordination bonds with one or more coordinating atoms or ions. The number of coordination bonds a ligand group forms with 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 action with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring through the metal center connection, so that the present invention can effectively provide dynamic metal-ligand actions with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:
Figure BDA0001936065950002312
wherein A is a coordinating atom or ion, M is a metal center, and an A-M bond formed by each ligand group and the same metal center is a tooth, wherein the A is connected by a single bond to represent that the coordinating atoms or ions belong 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 the group consisting of but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. Incidentally, sometimes a exists in the form of negative ions;
Figure BDA0001936065950002313
is a cyclopentadiene ligand. In the present invention, it is preferable that one coordinating atom or ion form only one coordination bond with one metal center, and therefore the number of coordinating atoms or ions contained in a ligand group is the number of teeth of the ligand group. The ligand group interacts with the metal-ligand formed by the metal center (as M-L)xRepresenting the number of ligand groups interacting with the same metal center) is related to the kind and number of coordinating atoms or ions on the ligand groups, the kind and valence of the metal center, and the like.
In embodiments of the invention, where supramolecular interactions crosslinks above the gel point are formed, one metal center must be capable of forming a metal-ligand interaction with at least two of the ligand groups (i.e., M-L) in order to be able to form crosslinks based on metal-ligand interactions2Structure) or a metal-ligand interaction may be formed by multiple ligands with the same metal center, where two or more ligand groups may be the same or different. The coordination number of one metal center is limited, and the more the coordinating atoms or ions of the ligand groups, the fewer the number of ligands that one metal center can coordinate, the lower the degree of supramolecular cross-linking based on metal-ligand interaction; however, since the more denticity each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, and thus, in the present invention, it is preferable that the number of ligand groups not exceed tridentate.
In embodiments of the invention, there may be only one ligand in a polymer chain or in a polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure, and a skeleton 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 connected to the polymer chain or the small molecule are different. Suitable ligand combinations can be effective in preparing polymers having specific properties, e.g., synergistic and/or orthogonal effects, enhancing the overall performance of the material. Suitable ligand groups (core ligand structures) may be exemplified by, but are not limited to:
examples of monodentate ligand groups are as follows:
Figure BDA0001936065950002321
bidentate ligand groups are exemplified as follows:
Figure BDA0001936065950002322
tridentate ligand groups are exemplified below:
Figure BDA0001936065950002323
tetradentate ligand groups are exemplified below:
Figure BDA0001936065950002324
the polydentate ligands are exemplified by:
Figure BDA0001936065950002325
in embodiments of the present invention, the metal center M may be the metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.
The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).
More preferably, the metal is a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), or a metal of the actinide series (Th). Further preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th are selected to obtain stronger dynamic property.
In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:
Figure BDA0001936065950002331
other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.
In the embodiment of the present invention, the metal inorganic compound is preferably an oxide or sulfide particle of the above metal, particularly a nanoparticle.
In embodiments of the present invention, the metal chelate compound which can provide a suitable metal center is preferably a chelate compound having a vacancy in a coordination site, or a chelate compound in which a part of the ligands can be substituted with the skeletal ligand of the present invention.
In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002332
the ionic interaction in the present invention refers to a supramolecular interaction which contains at least one pair of positively and negatively charged ionic groups in the polymer structure and is formed by coulomb force between the positive ionic group and the negative ionic group. The cationic group refers to a group having a positive charge, and examples thereof include:
Figure BDA0001936065950002341
preference is given to
Figure BDA0001936065950002342
The anionic group refers to a group having a negative charge, and examples thereof include:
Figure BDA0001936065950002343
preference is given to
Figure BDA0001936065950002344
Wherein the anionic groups may also be present in clay minerals including, but not limited to, kaolinite, antigorite, pyrophyllite, talc, montmorillonite, saponite, vermiculite, hydromicas, mica, chlorite, palygorskite, sepiolite. In special cases, the positive and negative ionic groups may be in the same compound structure, such as choline glycerophosphate, 2-methacryloyloxyethyl phosphorylcholine, l-carnitine, methacryloylethyl sulfobetaine, etc. The ionic action can be stably existed in the polymer, and the strength of the ionic action can be well controlled by changing the concentration and the kind of the ionic group.
In the embodiment of the present invention, the combination of the positive ionic group and the negative ionic group is not particularly limited as long as the positive ionic group can form a suitable ionic action with the negative ionic group. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002345
the ion-dipole effect in the present invention refers to a supramolecular effect formed by interaction between an electric dipole and a charged ionic group, wherein when two atoms with different electronegativities are bonded, the electric charge distribution is not uniform due to the induction of the atom with the greater electronegativity, resulting in asymmetric distribution of electrons. The ionic group may be any suitable charged group, such as the following, but the invention is not limited thereto:
Figure BDA0001936065950002346
preference is given to
Figure BDA0001936065950002347
Figure BDA0001936065950002348
The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O. The ion-dipole effect can stably exist in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of generating and dissociating the acting force are mild.
In the 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:
Figure BDA0001936065950002349
the host (represented by G) is a compound (small molecule or ionic group) which can be recognized by the host and embedded into the host cavity, one host molecule can recognize and bind a plurality of guest molecules, in the embodiment of the invention, one host molecule preferably recognizes and interacts with at most two guest molecules, the host molecules include but are not limited to ethers (including crown ether, cryptate ether, spherulite ether, semispherical ether, pod ether, lasso ether, benzocrown ether, heteroporocrown ether, heterocryptate ether, mixed cryptate ether), cyclodextrin, cyclophane, cucurbituril, calixarene, pillararene and suitable inorganic organic ionic frameworks, preferably crown ether, β -cyclodextrin, cucurbit [8] urea, calixarene, pillararene, and aromatic compounds including aromatic compounds, heterocyclic aromatic compounds, polycyclic aromatic compounds, and suitable long-chain aromatic compounds, which can form a stable ring structure under the conditions of host-guest molecules, long-chain ionic compounds, polycyclic aromatic compounds, and suitable long-chain aromatic compounds, which can form a stable ring structure under the normal conditions, long-chain aromatic compounds, polycyclic ionic compounds, polycyclic compounds, and suitable guest molecules.
Suitable host molecules may be exemplified by, but are not limited to:
Figure BDA0001936065950002351
Figure BDA0001936065950002352
Ni(PDC)(H2O)2skeleton, Zn3(PTC)2(H2O)8·4H2An O skeleton;
suitable guest molecules may be exemplified by, but are not limited to:
Figure BDA0001936065950002353
in the 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 a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002354
wherein, the term "metallophilic" as used in the present invention means when the two outermost electronic structures are d10Or d8The metal ions of (a) are brought closer to less than the sum of their van der waals radii; wherein, the two metal ions which have the effect of the metallophilic can be the same or different. The outermost electronic structure is d10Metal ions of (2) include, but are not limited to, Cu+、Ag+、Au+、Zn2+、Hg2+、Cd2+Preferably of Au+、Cd2+(ii) a The outermost electronic structure is d8Metal ions of (2) include, but are not limited to, Co+、Ir+、Rh+、Ni2+、pt2+、Pb2+Preferably Pt2+、Pb2+. The metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the supermolecule dynamics 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。
herein, the dipole-dipole effect in the present invention refers to that when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction of the atom with the greater electronegativity, resulting in asymmetric distribution of electrons, resulting in electric dipoles, and the interaction between the two electric dipoles. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effect may exhibit differences in supramolecular dynamics depending on temperature differences.
In the embodiment of the present invention, the combination between the electric dipoles is not particularly limited as long as an appropriate dipole-dipole action can be formed between the electric dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002361
among them, the halogen bond interaction in the present invention refers to a non-covalent interaction formed between a halogen atom and a neutral or negatively charged lewis base, and is essentially an interaction between a sigma-anti bond orbital of the halogen atom and an atom or pi-electron system having a lone electron pair. The halogen bond interaction can be represented by-X … Y-, wherein X can be selected from Cl, Br, I, preferably Br, I; y can be selected from F, Cl, Br, I, N, O, S, pi bond, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on the halogen bond effect, ordered and self-repairing polymers can be designed.
In the embodiment of the present invention, the combination of the atoms forming the halogen bond function is not limited as long as a stable halogen bond function 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-。
herein, the Lewis acid-base pair referred to in the present invention refers to a non-covalent interaction formed between a Lewis acid and a Lewis base. Wherein, the lewis acid refers to a substance (including molecules, ions or atomic groups) capable of accepting an electron pair, and can be selected from positive ion groups (such as alkyl positive ions, nitro positive ions, quaternary ammonium positive ions, imidazole positive ions and the like), metal ions (such as sodium ions, potassium ions, calcium ions, magnesium ions and the like), electron-deficient compounds (such as boron trifluoride, organoborane, aluminum chloride, ferric chloride, sulfur trioxide, dichlorocarbene, trifluoromethanesulfonate and the like), and the lewis acid is preferably alkyl positive ions, quaternary ammonium positive ions, imidazole positive ions, organoborane, and more preferably organoborane; the Lewis base refers to a substance (including a molecule, an ion or an atomic group) capable of giving an electron pair, which can be selected from the group consisting of an anionic group (such as a halide, an oxide, a sulfide, a hydroxide, a carbonate, a nitrate, a sulfate, a phosphate, an alkoxide, an olefin, an aromatic compound, etc.), a compound having a lone pair of electrons (such as ammonia, an amine, an imine, an azo compound, a nitroso compound, cyanogen, an isocyanate, an alcohol, an ether, a thiol, carbon monoxide, carbon dioxide, nitric oxide, nitrous oxide, sulfur dioxide, a compound having a lone pair of electrons, a salt of a compoundOrganophosphine, carbene, etc.), the lewis base is preferably an alkoxide, an alkene, an aromatic compound, an amine, an azo compound, a nitroso compound, an isocyanate, carbon dioxide, an organophosphine, and more preferably an amine, an azo compound, a nitroso compound, an organophosphine. Wherein, the Lewis acid-base pair action is preferably a 'hindered Lewis acid-base pair action', and the 'hindered Lewis acid-base pair action' means that at least one of Lewis acid and Lewis base in the Lewis acid-base pair action needs to be connected with a 'bulky group with steric effect'; said "bulky group with steric hindrance" can weaken the strength of coordination bond between Lewis acid and Lewis base, so that Lewis acid-base pair can exhibit strong supermolecule dynamics, and it is selected from C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl, most preferably from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl. Wherein the azo compound is preferably selected from azomethane, azotert-butane, N-methylazomethylamine, N-methylazoethylamine, N-ethylazoethylamine, azodiacetic acid, azobenzene, azodiphenylamine, dichloroazobenzene, azobisisobutyronitrile, azodicarbonamide, dimethyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate, di-tert-butyl azodicarboxylate; the nitroso compound is preferably selected from the group consisting of nitrosomethane, nitrosotert-butane, N-nitrosoethanolamine, nitrosobenzene, nitrosotoluene, nitrosochlorobenzene, nitrosonaphthalene, and N-nitrosourea. The Lewis acid-base pair has good dynamic reversibility and can be rapidly dissociated under the condition of slight heating or in the presence of an organic solvent, thereby realizingNow self-repairing or reshaping.
In the embodiment of the present invention, the combination of the formation of the action of the Lewis acid-base pair is not limited as long as a stable Lewis acid-base pair action can be formed in the polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001936065950002371
wherein, in the present invention, the cation-pi action refers to the non-covalent interaction formed between a cationic group and an aromatic pi system. There are three main classes of cation-pi action, the first group being simple inorganic cations or ionic groups (e.g. Na)+、K+、Mg2+、NH4 +、 Ca2+) And aromatic pi systems; the second group is the interaction between organic cations (e.g., quaternary ammonium cations) and aromatic pi systems; the third type is the interaction between positively charged atoms in dipole bonds (e.g., H atoms in N-H bonds) and aromatic π systems. The cation-pi effect has rich varieties and moderate strength, can stably exist in various environments, and can prepare polymers with rich performance based on the cation-pi effect.
In the embodiment of the present invention, the kind of the cation-. pi.function is not particularly limited as long as it can form a stable cation-. pi.function in the polymer. Some suitable cationic groups may be exemplified by, but are not limited to:
Figure BDA0001936065950002372
Na+、K+、Li+、Mg2+、Ca2+、Be2 +、H-O、 H-S、H-N。
wherein, in the present invention, anion-pi interaction refers to non-covalent interaction formed between an anionic group and an electron-deficient aromatic pi system. The anionic groups may be simple inorganic non-metallic ions or ionic groups(e.g., Cl)-、Br-、I-OH); or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system means that due to different electronegativities of ring-forming atoms, the density distribution of pi electron clouds of rings is not uniform, and pi electrons mainly deviate to the electronegativity high electron direction, so that the density distribution of the pi electron clouds of aromatic rings is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable identification, and can be used for constructing polymers with special properties.
In the embodiment of the present invention, the kind of the anion- π action is not particularly limited as long as it can form a stable anion- π action in the polymer. Some suitable anionic groups may be exemplified by, but are not limited to:
Figure BDA0001936065950002373
Cl-、Br-、I-、OH-、SCN-；
some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.
In the present invention, the benzene-fluorobenzene reaction refers to a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon, which is composed of the combination of dispersive force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The polymer with special function can be prepared by utilizing reversibility and stacking action of benzene-fluorobenzene action.
In the embodiment of the present invention, the kind of the benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:
Figure BDA0001936065950002381
wherein, the pi-pi stacking effect in the invention refers to the pi-pi stacking effect formed by overlapping pi-bond electron clouds in an aromatic pi system which can provide the pi-bond electron clouds in the polymer. Pi-pi stacking functions in three ways, including face-to-face stacking, offset stacking, and edge-to-face stacking. The surface accumulation means that the interactive ring surfaces are parallel to each other, the distance between the centers of the parallel ring surfaces is almost equal to the distance between the ring surfaces, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron-withdrawing property of a substituent group connected to the ring surfaces is relatively strong, the pi-pi action of the surface accumulation becomes relatively obvious; the offset accumulation means that the action ring surfaces are parallel to each other, but the center of the ring has certain offset, namely the distance of the center of the ring is larger than the distance between the ring surfaces, the accumulation mode relieves the mutual exclusion action between the two ring surfaces, correspondingly increases the attraction of sigma-pi, and is a common accumulation mode; stacking other than planar stacking and offset stacking is called edge-planar stacking, which has the smallest energy and the smallest intermolecular repulsion, and is often found between ring-conjugated molecules having smaller van der waals surfaces or between ring-conjugated molecules having flexible linkers.
Aromatic pi systems capable of providing pi-bonded electron clouds, including but not limited to most condensed ring compounds and some heterocyclic compounds in which pi-pi conjugation occurs, suitable aromatic pi systems may be exemplified by, but are not limited to, the following:
Figure BDA0001936065950002382
Figure BDA0001936065950002383
preference is given to
Figure BDA0001936065950002384
The pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.
In the embodiment of the present invention, the combination of the aromatic pi systems providing the pi-bond electron cloud 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:
Figure BDA0001936065950002385
the ionic hydrogen bonding in the invention is composed of a positive ionic group and a negative ionic group which can form hydrogen bonding, and simultaneously forms hydrogen bonding and coulomb interaction between positive ions and negative ions, or is composed of a positive/negative ionic group which can form hydrogen bonding and a neutral hydrogen bonding group, and simultaneously forms hydrogen bonding and ion-dipole interaction between positive ions and negative ions and the neutral group.
In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002391
herein, the radical cationic dimerization referred to in the present invention refers to a supramolecular interaction established by interaction between radical cationic groups containing both radical and cation. By way of example, the radical cationic groups that can form radical cationic dimerization include, but are not limited to, the following:
Figure BDA0001936065950002392
in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0001936065950002393
the phase separation in the present invention refers to an unstable tendency of separation between phases due to a change in a certain environmental condition in a multi-phase system, and includes phase separation caused during a supramolecular action such as coordination, recombination, assembly, combination, aggregation, etc., phase separation caused by an incompatible phase, phase separation caused by an incompatible block structure, etc.
In the embodiments of the present invention, the phase topology (phase morphology) formed by phase separation is not limited, and includes, but is not limited to, spherical, cylindrical, helical, lamellar, and combinations thereof. Any phase, including different phases, can be dispersed in another phase, can form interpenetrating double/multiple continuous phases with other phases, can be mutually independent continuous phases, and can also be in a mixed form. In the embodiment of the present invention, it is preferable that one phase is dispersed in the other phase in a spherical shape as phase-separated physical crosslinks, so that the polymer can more conveniently have better flexibility and elasticity.
The crystal as referred to in the present invention refers to a process in which polymer chains are arranged and folded to form ordered domains, and includes a crystal caused during a supramolecular action such as coordination, recombination, assembly, combination, aggregation, etc., a crystal caused by an incompatible phase, a crystal caused by an incompatible block structure, a crystal caused by a regular easy-to-crystallize segment, a crystal caused by a liquid crystal, etc. The liquid crystal chain segment is introduced, and crystallization caused by liquid crystal can be utilized to effectively regulate and control crystallization, so that dynamic reversible transformation can be realized under the stimulation conditions of heat, light, pH, chemical change and the like; wherein, the liquid crystal chain segment can be introduced by liquid crystal polymers (such as poly-p-benzamide, poly-p-phenylene terephthamide, poly-benzothiazole, poly-benzoxazole and the like), mesogens (such as 4, 4' -dimethoxyazobenzene, ethylene-p-methoxyphenyl terephthalate, mesogenic diacrylate and the like) and the like.
In the present invention, the phase separation and crystallization may be independent or may be simultaneously carried out by the same unit structure. The phase separation and/or crystallization not only has the functions of increasing the apparent molecular weight of the supermolecule and regulating the topological structure of the supermolecule and the microstructure of the polymer, but also has the self-reinforcing effect, and can improve the properties of the polymer, such as strength, modulus and the like.
In an embodiment of the present invention, the polymer having the phase separation/crystallization may be a segment based on the following polymer segments, groups, or any combination thereof, but is not limited thereto: amorphous polymer segments with high glass transition temperatures (i.e., glass transition temperatures above the upper limit of the material's operating temperature, typically above 40 ℃, preferably not less than 100 ℃), such as polystyrene, polymethylmethacrylate, polyvinylpyridine, hydrogenated polynorbornene, polyether, polyester, polyetheretherketone, polyaromatic carbonate, polysulfone, and the like; hydrogen bond group-rich polymer segments, groups such as polyamides, polypeptides, urea bond-rich segments, urethane bond-rich segments, ureido pyrimidinone-based segments, and the like; polymer segments, groups rich in crystalline phases, such as crystalline polyethylene, crystalline polypropylene, crystalline polyester, crystalline polyether, liquid crystal polymer, liquid crystal groups, and the like; ionic polymer segments such as polyacrylate, polymethacrylate, polyacrylamide, polystyrene sulfonate, and the like; polymer chain segments rich in conjugated structures, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, polythiophene and the like. Among them, amorphous polymer segments with high glass transition temperature, polymer segments/groups rich in hydrogen bonding groups, and polymer segments/groups rich in crystalline phases are preferred in order to design and control the molecular structure of the polymer to obtain the best performance.
In the present invention, one or more of the noncovalent interactions may be contained in the force-responsive polymer. When only one non-covalent action is contained, the polymer structure is relatively simple and the preparation is convenient; when multiple noncovalent interactions are involved, it is preferred that the multiple noncovalent interactions be orthogonal and/or synergistic. The orthogonality refers to that the formation, dissociation and other responses of the plurality of different non-covalent interactions do not influence each other; by synergy, it is meant that the formation and/or dissociation and/or other response of one or more of the different non-covalent interactions triggers the formation and/or dissociation and/or other response of the other non-covalent interactions or occurs simultaneously with the formation and/or dissociation and/or other response of the other non-covalent interactions and produces a greater effect than a linear superposition of the various non-covalent interactions. In the invention, reasonable design, selection and regulation can be carried out according to actual needs, and the force-induced responsive polymer with convenient preparation and remarkable non-covalent dynamic property is obtained.
In the embodiments of the present invention, the "non-covalent moiety" refers to a group or molecule or a structural unit for forming various types of non-covalent interactions, which includes, but is 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, polyfluorinated aromatic hydrocarbons, radical cationic groups, phase-separable polymer segments, crystalline polymer segments, and the like. The non-covalent moiety, which may be located at any suitable position on the force-responsive polymer, includes, but is not limited to, the crosslinked network backbone of the crosslinked polymer, the side chains/branches/branched chains backbone of the crosslinked polymer crosslinked network backbone, the side groups and/or end groups of the polymer, other components of the polymer such as small molecules, fillers, and the like.
In embodiments of the invention, when a plurality of the non-covalent motifs are present in the force-responsive polymer, they may be the same or different and may form the same or different non-covalent interactions.
In the present invention, non-covalent dynamicity refers to the reversible transformation process by which non-covalent interactions can take place in dissociated and recombined/associated states. The high non-covalent dynamic property enables the reversible transformation process to be fast in speed, and is beneficial to obtaining fast self-repairability. The noncovalent interaction in the present invention is preferably a noncovalent interaction having high binding strength and strong noncovalent dynamics. In addition, based on the non-covalent dynamic property, besides the self-repairing property, the force-induced responsive polymer can be endowed with other properties, such as directionality of halogen bond action, cation-pi action, anion-pi action, controllable selectivity and controllable identification on small molecules/ions/groups in host-guest action, benzene-fluorobenzene action, ordering of pi-pi stacking action, pH, concentration sensitivity and conductivity of ion action, ion-dipole action and ion hydrogen bond action, temperature sensitivity of dipole-dipole action, special photoelectricity of metallophilic interaction and free radical cation dimerization, and the like, and non-covalent elements can be reasonably selected according to requirements for molecular design, so that the force-induced responsive material is endowed with unique functional properties. These embody the benefits and inventive aspects of the present invention.
In embodiments of the invention, the component for attaching the force-sensitive moiety and/or the non-covalent moiety may be a small molecule linker and/or a polymer segment. Wherein said small molecule linking group refers to a small molecule hydrocarbon group having a molecular weight of not more than 1000Da, generally containing 1 to 71 carbon atoms, which may or may not contain a heteroatom group. In general terms, the small molecule hydrocarbyl group may be selected from any of the following groups, any unsaturated form, any substituted form, any hybridized form, and combinations thereof: c1-71Alkyl, ring C3-71Alkyl, phenyl, benzyl, aryl; wherein, the small molecule alkyl can also be selected from liquid crystal chain segment. The polymer chain segment includes, but is not limited to, a polymer chain segment whose main chain is a carbon chain structure, a carbon-hetero chain structure, a carbon element chain structure, an element-hetero chain structure, or a carbon-hetero element chain structure. The carbon chain structure is a structure of which the main chain skeleton only contains carbon atoms; the carbon heterochain structure is a main chain skeleton which simultaneously contains carbon atoms and any one or more hetero atomsThe structure of a molecule, wherein the heteroatoms include, but are not limited to, sulfur, oxygen, nitrogen; the carbon element chain structure is a structure that a main chain skeleton simultaneously contains carbon atoms and any one or more element atoms, wherein the element atoms comprise but are not limited to silicon, boron and aluminum; the element chain structure is a structure that a main chain skeleton only contains element atoms; the element heterochain structure is a structure which has a main chain skeleton and only contains at least one heteroatom and at least one element atom; the carbon-heteroatom chain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms, heteroatoms and element atoms.
In one embodiment of the present invention, the polymer segment is preferably a polymer segment whose main chain has a carbon chain structure or a carbon hetero chain structure, because of its abundant structure and excellent performance. By way of example, preferred carbon-and hetero-carbon-chain polymer segments include, but are not limited to, homopolymers, copolymers, modifications, derivatives, and the like of, for example, acrylic polymers, saturated olefinic polymers, unsaturated olefinic polymers, polystyrenic 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 segment is preferably an elemental heterochain structure, such as various types of polyorganosiloxane polymers, which generally have good corrosion resistance, oil and water resistance, high and low temperature resistance, and good tensile toughness.
In another embodiment of the present invention, the glass transition temperature of the polymer chain segment is preferably not higher than 25 ℃, which is expressed as flexibility at room temperature, so that the subsequent processing and preparation of the product at room temperature are facilitated, the flexible and viscous product is conveniently obtained, and the hardness of the material matrix is conveniently adjusted by increasing the crosslinking density or using other additives, so that the material matrix is used as a matrix, which is beneficial to expressing non-covalent dynamics, and obtaining self-repairing performance. In another embodiment of the present invention, it is preferable that the glass transition temperature of the polymer segment is higher than 25 ℃ but lower than 40 ℃ to facilitate the introduction of temperature sensitivity, moderate elasticity, and the like. In another embodiment of the present invention, the glass transition temperature of the polymer segment is preferably not lower than 40 ℃, which is advantageous for introducing the characteristics of shape memory, high-temperature dimensional stability, low-temperature and normal-temperature hardness, and the like. In another embodiment of the present invention, it is preferable that the glass transition temperature of the polymer segment is not lower than 100 ℃.
In embodiments of the present invention, the small molecule and/or polymer segment used to link the force-sensitive and/or non-covalent motif may have any suitable topology, including but not limited to linear structures, branched structures (including but not limited to star, H, dendritic, comb, hyperbranched), cyclic structures (including but not limited to single ring, multiple ring, bridge, grommet, wheel ring), two-dimensional/three-dimensional cluster structures, and combinations of two or any of them; among them, a linear structure which facilitates synthesis and control of the structure, a branched structure which is abundant in the structure, and a two-dimensional/three-dimensional cluster structure which can be locally reinforced are preferable, and a linear structure and a branched structure are more preferable. In the present invention, it is not even excluded to use the crosslinked polymer particles for further polymerization/crosslinking etc. reactions and linkages.
The various 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 molecule compounds, small molecule groups, and certain macromolecular compounds and macromolecular groups having a fixed structure, the molecular weight is generally monodispersed, i.e., has a fixed molecular weight; and for oligomers, polymers, oligomer residues, polymer residues, and the like having a polydisperse 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; the macromolecular compound and the macromolecular group refer to compounds or groups with molecular weight more than 1000 Da.
In the present invention, when the polymer is prepared, according to the actual requirements of the preparation process, the forming process, the use performance requirements and the like, the additives, the fillers and the swelling agents can be selectively added or used as the formulation components of the polymer, which can improve the material processing performance, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance, but the additives or the used substances are not necessary.
Wherein, the auxiliary agent can include but is not limited to one or a combination of several of the following, such as synthesis auxiliary agents, including catalysts and initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; the auxiliary agent for improving the mechanical property comprises a toughening agent and a coupling agent; the auxiliary agents for improving the processing performance comprise a solvent, a lubricant, a release agent, a plasticizer, a thickening agent, a thixotropic agent and a flatting agent; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; other auxiliary agents include antistatic agents, sterilization and mildew proofing agents, foaming agents, foam stabilizers, nucleating agents, rheological agents and the like.
In the present invention, the filler includes, but is not limited to, inorganic non-metallic fillers, organic fillers, and organometallic compound fillers.
The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, silica, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, black phosphorus nano sheet, molybdenum disulfide, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano Fe3O4Particulate, nano gamma-Fe2O3Particulate, nano MgFe2O4Particulate, nano-MnFe2O4Granular, nano CoFe2O4Granules,Quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)4：Er、CaF2：Er、Gd2(MoO4)3：Er、Y2O3：Er、Gd2O2S：Er、BaY2F8：Er、LiNbO3：Er，Yb，Ln、Gd2O2：Er，Yb、Y3Al5O12：Er，Yb、TiO2：Er，Yb、YF3：Er，Yb、Lu2O3：Yb，Tm、 NaYF4：Er，Yb、LaCl3：Pr、NaGdF4：Yb，
Figure BDA0001936065950002421
Core-shell nanostructure, NaYF4：Yb，Tm、Y2BaZnO5：Yb，Ho、NaYF4：Yb，
Figure BDA0001936065950002422
Core-shell nanostructure of Tm, NaYF4：Yb，
Figure BDA0001936065950002423
Core-shell nanostructures of (a), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers, and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the function of generating heat under the action of infrared and/or near infrared light is preferred, and includes but is not limited to graphene and oxygenGraphene, carbon nanotube, black phosphorus nanosheet and nano Fe3O4The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.
The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-CoPt3Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other nano metal particles capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic action; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.
The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.
The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.
Wherein, the type of the filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred3O4Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be selectively modified and then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the filler has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.
Wherein, the swelling agent can include but is not limited to water, organic solvent, ionic liquid, oligomer and plasticizer. The oligomers can also be regarded as plasticizers.
Wherein the ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1, 3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and also CF3SO3 -、(CF3SO2)2N-、C3F7COO-、 C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.
In the present invention, the force-responsive polymer may have one, two or more glass transition temperatures, or may not have a glass transition temperature. In a preferred embodiment of the present invention, the force-responsive polymer has at least one glass transition temperature higher than 100 ℃, and more preferably all glass transition temperatures higher than 100 ℃, and the obtained force-responsive polymer has good dimensional stability, mechanical strength and high temperature resistance, and is suitable for application scenarios with high requirements on stress bearing and rigidity; in another preferred embodiment of the invention, at least one of the glass transition temperatures of the force-responsive polymer is between 25 and 100 ℃, and more preferably all the glass transition temperatures of the force-responsive polymer are between 25 and 100 ℃, so that polymer products in the forms of ordinary solid, foam, gel and the like can be conveniently prepared at room temperature, and the force-responsive polymer is suitable for application scenarios with higher requirements on mechanical strength and toughness; in another preferred embodiment of the present invention, the force-responsive polymer has at least one glass transition temperature lower than 25 ℃, more preferably lower than 25 ℃ and most preferably lower than 0 ℃, and the obtained force-responsive polymer has good flexibility, is favorable for being used at room temperature and low temperature, is also favorable for being used as materials such as elastomers, gels, foams and common solids, and is favorable for exhibiting the properties such as stress sensitivity, non-covalent dynamics, self-repairing, etc. In the present invention, it is preferred that the force responsive polymer has a glass transition temperature of at least one, and more preferably all, below 25 ℃. The force-responsive polymer has better flexibility and creep property when the glass transition temperature of the force-responsive polymer is lower than 25 ℃.
In the embodiment of the invention, the form of the force-responsive polymer can be common solid, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), elastomer, foam material and the like, wherein the content of soluble small molecular weight components in the common solid and the foam material is generally not higher than 10 wt%, and the content of small molecular weight components in the gel is generally not lower than 50 wt%. The shape and volume of the common solid are fixed, the common solid has better mechanical strength and can not be restrained by an organic swelling agent or water. Elastomers have the general properties of ordinary solids, but at the same time have better elasticity and are softer. The gel is generally higher in softness and lower in solid content, and the swelling agent has the functions of conduction, conveying and the like and has outstanding advantages. The foam material has the advantages of low density, lightness and high specific strength, can overcome the problems of brittleness of part of common solids and low mechanical strength of organogel, and has good elasticity and soft and comfortable characteristics. 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 crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer, and an ionic liquid), or may be obtained by swelling with a swelling agent after the polymer is prepared. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.
In the preparation process of the polymer, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted for foaming.
The mechanical foaming method is that a large amount of air or other gases are introduced into emulsion, suspension or solution of polymer by means of strong stirring in the preparation process of the polymer to form uniform foam, and then the uniform foam is formed into foam material through physical or chemical change. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.
Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into the material and then compounded to form closed cell foamed polymer; (5) a filling expandable particle method of mixing filling expandable particles and expanding the expandable particles during molding or mixing to actively foam the polymer material; among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer. The physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like. In addition, the preparation method can also adopt a freeze drying method.
The chemical foaming method is a method for generating gas and foaming along with chemical reaction in the process of foaming polymer, and includes, but is not limited to, the following two methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. And (2) a foaming method in which the polymer components interact with each other to generate a gas, that is, a chemical reaction between two or more components in a foaming system is used to generate an inert gas (such as carbon dioxide or nitrogen) to expand the polymer and thus foam the polymer. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.
In the preparation process of the polymer, a person skilled in the art can select a proper foaming method and a foam material forming method to prepare the foam material according to the actual preparation situation and the target polymer performance.
In an embodiment of the present invention, the structure of the polymer foam material relates to three structures 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 communicated with each other or completely communicated with each other, gas or liquid can pass through the single dimension or the three dimensions, and the cell diameter is different from 0.01 to 3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from each other by a wall membrane, most of the inner cells are not communicated with each other, and the cell diameters are different from 0.01 mm to 3 mm. The contained cells have a structure which is not communicated with each other, and the structure is a semi-open cell structure. For a foam structure which has been formed into closed cells, it can also be made into an open cell structure by mechanical pressing or chemical methods, and the skilled person can select them according to the actual needs.
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 a modulus of elasticity of less than 70MPa at 23 ℃ and 50% relative humidity; (2) a 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 above categories, having a modulus of elasticity between 70MPa and 700 MPa.
In embodiments of the present invention, the polymer foam materials may be further classified by their density into low-foaming, medium-foaming and high-foaming. Low-foaming foams having a density of more than 0.4g/cm3The foaming multiplying power is less than 1.5; the medium-foamed foam material has a density of 0.1-0.4 g/cm3The foaming ratio is 1.5-9; and a high-foaming foam material having a density of less than 0.1g/cm3The expansion ratio is greater than 9.
Those skilled in the art can select suitable foaming method and forming method to prepare the polymer foam product according to actual conditions and requirements.
In the invention, based on the single-hybrid network structure of the force-induced responsive polymer and the force-sensitive groups and non-covalent actions contained in the single-hybrid network structure, the polymer material can be provided with good structural support and mechanical properties, and can also obtain the force-induced responsiveness and non-covalent dynamics, so that the polymer coating, the adhesive, the fiber, the film, the plate, the elastomer, the gel, the foam and other materials with good force-induced responsiveness and self-repairing performance are prepared, and therefore, the stress, deformation, structural damage and failure processes of the polymer material are detected, monitored and warned, and when the structural damage occurs to the material, the good self-repairing performance can also be obtained; the preparation method has wide application prospect, and particularly shows remarkable application effect in the fields of functional coatings, buildings, medical treatment, chemical industry, household appliance manufacturing, automobile industry, bionics, energy, intelligent materials and the like.
For example, the mechanochromic, mechanoluminescent/phosphorescent properties based on mechanolponic polymers are applicable to information recording/storage, anti-counterfeiting and smart palette materials; the force-induced responsive polymer can also be coated in a base material, so that the attractive effect can be achieved, and when the base material deforms, the force-sensitive groups in the base material can be activated, the conditions of stress, deformation, distortion, damage and the like in the material can be fed back, and the prevention and later-stage optimization are facilitated; the polymer sealing compound with the stress sensing function and various sealing elements such as a sealing plug and a sealing ring can also be prepared, and the polymer sealing compound is applied to the aspects of electronic appliances, pipeline sealing and the like, reflects the stress condition of the material through the change of the color of the material, and plays the roles of stress monitoring and warning.
For another example, based on the non-covalent dynamic property of the force-induced responsive polymer and/or the force responsiveness with reversible force-induced activation characteristic, good self-repairing performance is obtained, and the force-induced responsive polymer material with self-repairing and recyclable use is suitable to be prepared, such as a binder with self-repairing performance, and is applied to the adhesion of various materials, such as the electrode adhesion in a battery and a capacitor, when the electrode has tiny cracks or damages, stress is generated to act on the binder, and a force sensitive group in the binder is subjected to force activation, plays a stress warning role and obtains better self-repairing performance, so that the purposes of increasing the reliability of a microelectronic product and prolonging the service life are achieved; the force sensitive group covalent crosslinking with non-covalent crosslinking effect and reversible force-activated characteristic is used as a temporary crosslinking point and is combined with common covalent crosslinking in a polymer to obtain a shape memory material, so that personalized and customized articles can be prepared and applied to specific occasions, such as shape memory medical instruments, orthoses, portable containers and the like which are convenient, comfortable and can be repeatedly used.
In addition, the force-responsive polymer of the present invention can be applied to other various suitable fields according to the performance of the polymer, and those skilled in the art can expand and implement the polymer according to the actual needs.
Example 1
Figure BDA0001936065950002441
Taking 3 molar equivalents of carboxyl-terminated four-arm polyethylene glycol (molecular weight is 2000), 15 molar equivalents of N-hydroxysuccinimide and 15 molar equivalents of dicyclohexylcarbodiimide, placing the mixture in a reaction vessel, dissolving the mixture with a proper amount of tetrahydrofuran, stirring the mixture at room temperature under a nitrogen atmosphere for reaction for 12 hours, adding 3 moles of a single compound (a) and 3 moles of a single compound (b), continuing stirring the mixture at room temperature for reaction for 24 hours, and removing impurities and a solvent after the reaction is finished to obtain a crosslinked polymer; then 40g of the purified product is swelled in a large amount of purple litmus aqueous solution to reach swelling equilibrium, and a polymer hydrogel can be obtained. The tensile strength of the gel was measured to be 1.68MPa and the elongation at break was 955%. When the gel is subjected to a tensile test, the gel gradually turns red along with the increase of tensile deformation, and the gel emits blue fluorescence when the gel is continuously stretched, because under the action of a mechanical force, heterolytic force sensitive groups in the gel are firstly subjected to force activation to generate sulfonic acid groups, and the sulfonic acid groups interact with a litmus reagent to cause the color of the gel to turn red; on further extension, the spirooxazine group in the gel will also be activated, causing a change in the fluorescent form. The sequential color and fluorescence change can well feed back and warn the stress of the material, and the stress sensor material can be used as a stress sensor material.
Example 2
Figure BDA0001936065950002451
Taking 0.5 molar equivalent of lateral group carboxyl polysiloxane (a), 10 molar equivalent of single compound (b), 5 molar equivalent of single compound (c) and 30 molar equivalent of single compound (d), placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of acetonitrile, adding 60 molar equivalent of dicyclohexylcarbodiimide and 20 molar equivalent of 4-dimethylaminopyridine, stirring the mixture at room temperature for reaction for 36 hours, placing the product into a mold, drying the product in a vacuum oven at 90 ℃ for 6 hours, and slowly cooling the product to the room temperature to obtain the polymer elastomer. Under the action of mechanical force, the non-covalent force sensitive groups in the elastomer are stressed and activated to cause fluorescence change; and the triaryl sulfur salt series force sensitive groups can generate phenyl cation after being stressed and activated, and react with nucleophilic secondary amino in the side group to obtain a crosslinking effect, thereby being beneficial to improving the strength of the material. The pi-pi stacking effect of the elastomer can also provide certain self-repairing performance when the elastomer breaks down. The elastic body in the embodiment can be used as a safety auxiliary material with force-induced fluorescence change and force-induced enhancement functions, not only can the stress of the material be fed back through fluorescence change, but also the mechanical strength can be spontaneously improved, and good practicability is achieved.
Example 3
Figure BDA0001936065950002452
80g of polyvinyl chloride, 4mol of 4-mercaptophenyl acid, 6mol of potassium carbonate and 1.5mol of tetrabutylammonium bromide are taken and placed in a reaction vessel, dissolved by a proper amount of cyclohexane, and then stirred and reacted for 3 hours at 65 ℃ to prepare the modified polyvinyl chloride (a) with the grafting rate of 16 mol%. 0.5mol of 5- (benzylamino) pentan-1-ol is taken to be arranged in a reaction vessel, dilute hydrochloric acid is dripped to adjust the pH value to 6, and the obtained solution is added into saturated NH4·PF6In the solution, compound (b) is obtained. 40g of modified polyvinyl chloride (a), 0.005mol of the compound (b), 0.005mol of the compound (c), 0.01mol of the compound (d) and 0.01mol of the compound (e) were mixed and the mixture was subjected to the above-mentioned reactionPutting the materials into a reaction vessel, dissolving the materials with a proper amount of tetrahydrofuran, adding a proper amount of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and stirring and reacting for 36 hours at room temperature under a nitrogen atmosphere to obtain the cross-linked modified polyvinyl chloride. Taking 50 parts of cross-linked modified polyvinyl chloride, adding a proper amount of chloroform, stirring and swelling for 30min, then adding 95 parts of epoxidized soybean oil, 1.5 parts of antioxidant BHT, 5 parts of liquid metal gallium and 25 parts of tricresyl phosphate, uniformly mixing, placing the mixture in a mold, naturally drying for 24h, and then drying under reduced pressure for 24h to obtain the plasticizer swelling gel. The gel is flexible and can be stretched and expanded in a large range, when a gel sample is stretched to a large deformation, the color of the gel sample can be changed into blue-green, and the slope of a stress-strain curve can be gradually increased, which is expressed as the increase of strength. Because the force sensitive groups in the two cross-linked networks are activated by force, the generated maleimide groups and sulfhydryl anions can generate further cross-linking action, and the mechanical strength of the material is improved. And when the gel sample is damaged, gel repair can be realized based on the reversible characteristic of the force sensitive group and the non-covalent dynamics of the host-guest action. The gel material in this embodiment is suitable for use as a thermally conductive sealing material with stress warning and force-induced enhancement functions.
Example 4
Figure BDA0001936065950002453
The polysiloxane (a) is prepared by taking toluene as a solvent, taking phenylhydrosiloxane-dimethylsiloxane copolymer (the content of a silicon-hydrogen bond is 50%) and acrylic acid as raw materials, taking a xylene solution of Karstedt catalyst as a catalytic system, and stirring and reacting at 85 ℃ for 10 hours. Placing 0.05 molar equivalent of polysiloxane (a), 2 molar equivalent of compound (b) and 6 molar equivalent of compound (c) in a reaction vessel, dissolving with a proper amount of dichloromethane, adding 40 molar equivalent of diisopropylcarbodiimide and 4 molar equivalent of 4-dimethylaminopyridine, stirring at room temperature for reaction for 24 hours, and removing impurities and solvent after the reaction is finished to obtain a purified product; and then 20g of the obtained product is taken to swell in 150mL of ethanol, 25mL of 0.15g/mL zinc dichloride ethanol solution is dropwise added under stirring, 8mL of triethylamine is added after the dropwise addition is finished, the stirring is carried out for 12 hours at room temperature, and then impurities and solvents are removed to prepare the common polymer solid. The solid sample has high mechanical strength and tensile toughness. In the slow stretching process, the sample can be firstly changed into green, because under the condition of low stretching deformation, the homolytic force sensitive groups are firstly stressed and activated to generate color change; when the stretching is continued, the dioxetane group in the polyester can be activated by force and emits red light through energy transfer. The sequential mechanochromism and mechanoluminescence processes can well feed back stress/deformation information and stress overload conditions of the material. And after the sample is cracked and damaged, the good self-repairing performance can be obtained based on the contained force sensitive groups and the reversible characteristic of non-covalent crosslinking. The solid polymer material can be used as a sealing material with a stress warning function and self-repairing performance.
Example 5
Figure BDA0001936065950002461
Taking 0.8 mol of single-amount side-mercapto polysiloxane (a), 6mol of single-amount compound (b), 12 mol equivalent compound (c) and 10 mol of single-amount compound (d), placing the materials in a reaction vessel, dissolving the materials with a proper amount of toluene, adding 30 mol equivalent triethylamine catalyst, stirring the materials at room temperature for reaction for 12 hours, adding 3 wt% of silicon carbide, 1.2 wt% of graphene and 13.2 mol equivalent cuprous iodide, uniformly mixing, placing the materials in a vacuum oven at 50 ℃ for heat preservation for 6 hours, and obtaining the polymer elastomer after the solvent is completely volatilized. The elastomer has low glass transition temperature, and has good low temperature resistance, barrier property and thermal conductivity. When the elastic body is stretched, the elastic body can emit red phosphorescence under the illumination of 350nm, and the phosphorescence intensity is in direct proportion to deformation. Based on the reversible characteristics of the side group tetradentate hydrogen bond crosslinking and the double-selenium force sensitive group contained in the elastomer, the force sensitive group can also be endowed with good self-repairing performance. The elastomer in this embodiment is suitable for use as a stress/strain sensor material.
Example 6
Figure BDA0001936065950002462
Taking benzoin dimethyl ether as a photoinitiator, and grafting and modifying polybutadiene with double end-capped hydroxyl groups by using 2-bromoethanethiol to obtain brominated polybutadiene (a); taking 0.5 molar equivalent of brominated polybutadiene (a), 4 molar equivalent of compound (b), 4 molar equivalent of compound (c), 12 molar single amount of compound (d), 5 wt% of glass microfiber, 0.5 wt% of sodium dodecyl benzene sulfonate and 0.5 wt% of antioxidant BHT, putting the materials into a reaction vessel, adding a proper amount of chloroform solvent, fully mixing, adding 45 molar equivalent of pyridine catalyst, stirring at room temperature for reaction for 5 hours under nitrogen atmosphere, and then keeping the temperature in a vacuum oven at 60 ℃ for drying for 8 hours to obtain the fiber reinforced elastomer. The elastomer sample has good mechanical strength, tensile toughness and rebound resilience. The sample can emit different fluorescence according to different tensile or compressive stress, the stress magnitude can be visually indicated, and the sample can be used as a stress sensor material. After the composite force sensitive groups in the elastomer are stressed and activated, the force-induced toughening effect can be obtained, and based on the tethered composite structure in the composite force sensitive groups, the covalent crosslinking degree can be kept from being reduced, and good structural stability is shown. And the lateral group in the crosslinking network is crosslinked by hydrogen bond, so that the local self-repairing performance can be provided for the polymer.
Example 7
Figure BDA0001936065950002463
Reacting N- (6-hydroxyhexyloxy) azobenzene with excessive acryloyl chloride by taking triethylamine as a catalyst and dichloromethane as a solvent to prepare azobenzene acrylate (a); taking 50 molar equivalents of azobenzene acrylate (a), 50 molar equivalents of acrylic acid and 0.05 molar equivalents of AIBN, placing the mixture in a reaction vessel, dissolving the mixture by using a proper amount of tetrahydrofuran, then stirring and reacting the mixture for 24 hours at 70 ℃ under nitrogen atmosphere, and after the reaction is finished, purifying the mixture to obtain an azobenzene side group polyacrylate copolymer; taking 0.4 molar equivalent of the polyacrylate copolymer, 4 molar equivalent of the compound (b) and 1 molar equivalent of the compound (c), placing the mixture in a reaction vessel, dissolving the mixture with a proper amount of acetonitrile, then adding 40 molar equivalent of diisopropylcarbodiimide and 4 molar equivalent of 4-dimethylaminopyridine, stirring the mixture at room temperature for reaction for 24 hours, then adding 8.6 wt% of column [6] arene, continuing stirring the mixture for reaction for 3 hours, and placing the obtained product in a vacuum oven at 60 ℃ for drying for 6 hours to obtain the common solid of the polymer. Gradient change of mechanical strength and modulus of the force-responsive polymer can be realized by controlling incident light intensity and irradiation position, so that the polymer can have a gradual force-induced color change effect under the same mechanical force action, and can be used as a stress warning material.
Example 8
Figure BDA0001936065950002471
Taking 70 molar equivalent of 5-norbornene-2-carboxylic acid (2-bromoethyl) ester and 10 molar equivalent of 5-norbornene-2-formamide, dissolving with proper amount of chlorobenzene, introducing nitrogen, carrying out bubbling to remove oxygen for 30min, and adding proper amount of ReCl5Stirring and reacting chlorobenzene solution of a catalyst for 1h under nitrogen atmosphere to obtain bromine-containing polynorbornene (a); taking 0.25 molar equivalent of bromine-containing polynorbornene (a), 0.75 molar equivalent of compound (b), 0.75 molar equivalent of compound (c) and 3 molar equivalents of 1, 6-hexanedithiol, putting the components into a reaction vessel, dissolving the components with a proper amount of dichloromethane, adding 12 molar equivalents of pyridine catalyst, stirring the mixture for reaction for 8 hours at room temperature under nitrogen atmosphere, and after the reaction is finished, drying the mixture in vacuum to remove the solvent to obtain the polynorbornene elastomer. The elastic body sample is slowly stretched, and the color of the elastic body sample can be sequentially changed from colorless transparency to pink color and blue color along with the increase of the tensile force, so that the stress condition of the material can be conveniently fed back through the color change. When the material is acted by a large force, the two kinds of homolytic force sensitive groups are both stressed and activated to generate free radicals, so that the color change is obtained, and the conductivity of the material can be improved. The elastomer material also has good self-repairing performance and shape memory function, and can be used as a multifunctional intelligent sensing material.
Example 9
Figure BDA0001936065950002472
Taking 110 molar equivalent of 5-norbornene-2-carboxylic acid (2-bromoethyl) ester, dissolving with proper amount of chlorobenzene, introducing nitrogen gas for bubbling to remove oxygen for 30min, and adding proper amount of ReCl5Stirring and reacting chlorobenzene solution of a catalyst for 1h under nitrogen atmosphere to obtain bromine-containing polynorbornene (a); dissolving 1 molar equivalent of polynorbornene (a) in dichloromethane, cooling in an ice bath for 30min, slowly dropwise adding 3 molar equivalents of m-chloroperoxybenzoic acid, stirring for reacting for 15min after dropwise adding, adding a proper amount of sodium carbonate aqueous solution to terminate the reaction, and purifying to obtain the alkene partially epoxidized polynorbornene (b) after the reaction is finished; taking 0.5 molar equivalent of polynorbornene (b), 4 molar equivalent of bis (2-hydroxyethyl) but-2-acetylenedicarboxylate, 8 molar equivalent of methyl 3- ((3-hydroxypropyl) dimethylammonio) propionate and 12 molar equivalent of compound (c), placing the materials in a reaction vessel, dissolving the materials with an appropriate amount of acetonitrile, adding 49 molar equivalents of potassium carbonate, reacting at room temperature for 16h, and removing impurities and solvent after the reaction is finished to obtain the polynorbornene elastomer. When the elastomer is slowly stretched, the fluorescence of the elastomer excited by 350nm ultraviolet light is changed from blue to yellow along with the increase of the stretching stress, and the fluorescence property is changed because the non-covalent single force sensitive groups in the elastomer are firstly stressed and activated; the tensile stress is continuously increased, the stress-strain curve fluctuates and shows that the strength is increased, because the covalent single force sensitive group in the elastic body is also stressed and activated to generate a carbonyl ylide intermediate which can react with the butynedioic ester group in the network framework to obtain further crosslinking action and improve the mechanical strength of the elastic body. The elastomer material can be used as a safety cable, a safety auxiliary material and the like with a visual stress warning function and a stress enhancing function. In addition, when the elastomer is subjected to crack damage, the ionic action of the elastomer can provide local self-repairing performance.
Example 10
Figure BDA0001936065950002481
Using acetonitrile as a solvent, and carrying out stirring reaction on N-bromoethyl maleimide and 2- (hydroxymethyl) furan in an equimolar ratio for 12 hours at 40 ℃ under a nitrogen atmosphere to obtain an intermediate product I; then taking tetrahydrofuran as a solvent, and stirring and reacting the intermediate product I and excessive phosgene at room temperature for 24 hours under a nitrogen atmosphere to obtain an intermediate product II; dissolving 80 molar equivalents of ethyl glyoxylate in dichloromethane, adding 0.2 molar equivalent of triethylamine catalyst, stirring at-20 ℃ for 2 hours, adding 0.5 molar equivalent of intermediate product II and 1 molar equivalent of triethylamine, heating to room temperature, stirring at room temperature for 20 hours, and removing impurities and solvent after the reaction is finished to obtain the homopolymer (a). Taking 0.2 molar equivalent of homopolymer (a), 1.8 molar equivalent of single compound (b), 5 molar equivalent of compound (c) and 3.5 molar equivalent of compound (d), placing the materials in a reaction vessel, dissolving with a proper amount of DMF, introducing nitrogen, bubbling, deoxidizing for 30min, adding 14 molar equivalent of pyridine catalyst, stirring and reacting at room temperature for 12h under nitrogen atmosphere, and removing impurities and solvents after the reaction is finished to obtain a polymer solid. When the sample is slowly stretched to a certain deformation, the color of the sample can be changed into purple, and the color is changed because the tandem composite force sensitive groups are activated by force; when the sample is continuously stretched to a large deformation, the sample can be locally degraded, and the covalent single force sensitive groups in the polymer are activated by force to generate furan groups, so that the degradation of the polymer is promoted. The solid sample also has good water resistance and oil resistance, and can be used as an environment-friendly packaging material with a stress warning effect or an environment-friendly lunch box.
Example 11
Figure BDA0001936065950002482
Taking benzoin dimethyl ether as a photoinitiator, and carrying out 365nm ultraviolet illumination reaction on phenyl double-ended polybutadiene and 2-aminoethanethiol for 30min under nitrogen atmosphere to obtain amino side group modified polybutadiene (a); taking 0.5 molar equivalent polybutadiene (a), 4 molar equivalent 1, 8-suberic acid, 10 molar equivalent compound (b), 3 molar equivalent compound (c) and 3 molar equivalent compound (d), placing the materials in a reaction vessel, dissolving the materials with a proper amount of dichloromethane, adding 45 molar equivalent N-hydroxysuccinimide and 45 molar equivalent dicyclohexylcarbodiimide, stirring and reacting for 36 hours at room temperature under a nitrogen atmosphere, adding 5 wt% of cellulose nanocrystal, stirring and mixing uniformly, placing the mixture in a mold, and drying for 3 hours in a vacuum oven at 80 ℃ to obtain the polybutadiene elastomer. The elastomer has good tensile toughness, tear resistance and heat conductivity. When the elastic body is slowly stretched to be greatly deformed, the color of the elastic body is changed into red; when the material is continuously stretched, the covalent single force sensitive groups are also stressed and activated, and generate a force-induced crosslinking effect through the reaction of the hybrid DA, so that the mechanical strength of the material is improved. The elastomer material in the present embodiment is suitable as a stress warning material with high reliability.
Example 12
Figure BDA0001936065950002483
Taking 1.1 mol of single-amount copolyether diamine (a) (with the molecular weight of 5000), 0.2 mol of single-amount compound (b), 0.2 mol of single-amount compound (c) and 1mol of trimesic acid, putting the materials into a reaction vessel, dissolving with an appropriate amount of acetone, adding 3.3 mol of single-amount N-hydroxysuccinimide and 3.3 mol of single-amount dicyclohexylcarbodiimide, stirring at room temperature under a nitrogen atmosphere for reaction for 36 hours, pouring the product into a mold after the reaction is finished, and drying in a vacuum oven at 60 ℃ for 6 hours to obtain the common solid of the polymer. The tensile strength of the solid was measured to be 17.3MPa, and the elongation at break was 124%. When the sample is slowly stretched, the sample can become light red hydrazone color, and the stress-strain curve fluctuates when the sample is continuously stretched, which is represented as the increase of strength, because after two force sensitive groups in the polymer are subjected to force activation, the generated active groups can generate further crosslinking reaction, and the force-induced enhancement effect is obtained. In addition, when a sample has cracks, the polymer can also provide better self-repairing performance for the polymer together based on the dynamic covalent characteristics of the contained force sensitive groups and the non-covalent dynamics of the skeleton amide hydrogen bond crosslinking and phase separation effects. Based on the above properties, it can be used as a mechanical part having stress enhancement and stress warning functions.
Example 13
Figure BDA0001936065950002491
80g of polyvinyl chloride, 4mol of 4-mercaptophenyl acid, 6mol of potassium carbonate and 1.5mol of tetrabutylammonium bromide are taken and placed in a reaction vessel, dissolved by a proper amount of cyclohexane, and then stirred and reacted for 3 hours at 65 ℃ to prepare the carboxyl modified polyvinyl chloride (a) with the grafting rate of 16 mol%. Taking 40g of modified polyvinyl chloride (a), 0.01mol of compound (b), 0.01mol of compound (c) and 0.01mol of compound (d), placing the materials in a reaction vessel, dissolving the materials with a proper amount of tetrahydrofuran, adding a proper amount of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring and reacting for 36h at room temperature under nitrogen atmosphere, adding 0.8g of metal osmium heteroaromatic ring particles and 0.2g of sodium dodecyl benzene sulfonate, stirring and mixing for 3h, placing the mixed material in a mold, and carrying out heat preservation and drying for 6h in a vacuum oven at 80 ℃ to obtain the common polymer solid. When the sample is stretched, the sample can emit blue light to visually feed back the stress of the material; when the material is continuously stretched, the tethered composite force sensitive groups in the material can be stressed and activated to obtain a certain toughening effect, and based on the non-chain-breaking property of the material, the structural stability can be continuously provided for the material, and the further damage of the material is delayed. The polymer solid material in the embodiment is suitable for serving as a supporting frame material with high reliability, is particularly suitable for application scenes such as mine hole operation, tunnel construction, offshore operation and the like with poor light, and can be used for facilitating maintainers to sense stress of the material and improving the use safety of the material based on the characteristics of mechanoluminescence and force-induced toughening.
Example 14
Figure BDA0001936065950002492
Taking 1 molar equivalent of carboxyl modified polyether ketone compound (a), 16 molar equivalent of compound (b), 2 molar equivalent of compound (c) and 2 molar equivalent of bis (2-hydroxyethyl) succinamide, putting the materials into a reaction container, adding a proper amount of DMF solvent, stirring and dissolving, adding 30 molar equivalent of dicyclohexylcarbodiimide and 5 molar equivalent of 4-dimethylaminopyridine, stirring and reacting for 24 hours at room temperature, putting the product into a mold, and drying in a vacuum oven at 110 ℃ for 6 hours under a heat preservation condition to obtain the common polymer solid. The solid sample has the characteristics of high surface hardness, good heat resistance, stable size and the like. Applying stress to the sample to bend the sample, wherein the fluorescence of the sample under 372nm excitation can be changed from sky blue to yellow under lower bending strain; when the bending strain is further increased, the color of the material can be changed into orange red, the sequential fluorescence and color change can well feed back the bending stress and the deformation of the material, and the material can be used as a polymer plate with a deformation detection function.
Example 15
Figure BDA0001936065950002493
Triethylamine is used as a catalyst, dichloromethane is used as a solvent, and a compound (a) and a compound (b) respectively react with excessive 4-vinylbenzoyl chloride to prepare a cross-linking agent I and a cross-linking agent II. Taking 50 molar equivalents of 4-vinylbenzyl acetate, 50 molar equivalents of 2, 3, 4, 5, 6-pentafluorostyrene, 5 molar equivalents of divinylbenzene, 2 molar equivalents of a crosslinking agent I, 2 molar equivalents of a crosslinking agent II, 5 wt% of multi-arm carbon nanotubes, 3 wt% of nano-silver particles and 0.25 wt% of fatty alcohol polyoxyethylene ether, putting the materials into a reaction vessel, adding 300 wt% of toluene solvent and 0.5 molar equivalent of azodimethoxyisoheptonitrile, stirring and mixing uniformly, stirring and reacting at 40 ℃ for 72 hours under a nitrogen atmosphere, and obtaining the polymer organogel after the reaction is finished. Under the action of mechanical force, two composite force sensitive groups are stressed and activated, so that the color of the two composite force sensitive groups can be changed into mauve, and a better force-induced toughening effect can be obtained. In addition, the tethered composite structure based on the composite force sensitive group ensures that the covalent crosslinking degree is not reduced after the tethered composite structure is activated, and can provide good structural stability. The gel material also has good thermal conductivity and antibacterial property, and can be used as a toy material with a force-induced color change effect and a force-induced toughening effect.
Example 16
Figure BDA0001936065950002501
Taking stannous octoate as a catalyst, pentaerythritol as an initiator and anhydrous toluene as a solvent, and carrying out ring-opening polymerization on lactide at 160 ℃ for 6h under nitrogen atmosphere to obtain the hydroxyl-terminated star-shaped polylactide. Taking 6 molar equivalents of star-shaped polylactide, 2 molar equivalents of the compound (a), 8 molar equivalents of the compound (b) and 2 molar equivalents of the compound (c), placing the star-shaped polylactide, the compound (a), the compound (b) and the compound (c) in a reaction container, dissolving the star-shaped polylactide, the compound (c) in a proper amount of dichloromethane, adding 48 molar equivalents of dicyclohexylcarbodiimide and 12 molar equivalents of 4-dimethylaminopyridine, stirring the mixture at room temperature for reaction for 36 hours, adding 120 wt% of acetyl tributyl citrate, 40 wt% of tributyl citrate and 5 wt% of nano palladium, uniformly mixing, pouring the mixed material into a mold, and drying the mixed material in a vacuum oven at 70 ℃ for 6 hours to obtain the plasticizer swelling gel. The gel sample was found to have a tensile strength of 4.46MPa and an elongation at break of 635%. When the gel is stretched, it can generate blue fluorescence, because the covalent single force sensitive group based on the bending activation mechanism is activated by force to generate strong fluorescence anthracene-based derivative. After the gel sample is damaged, the gel sample is repaired by direct heating, and is remotely heated and repaired by near infrared light irradiation based on the near infrared light thermal effect of the gel. Based on the abundant properties, the gel material can be used as a packaging material having a deformation warning function and self-repairing properties.
Example 17
Figure BDA0001936065950002502
Taking stannous octoate as a catalyst, ethanol as an initiator and anhydrous toluene as a solvent, and carrying out ring-opening polymerization on lactide at 160 ℃ for 6h under nitrogen atmosphere to obtain the hydroxyl-double-terminated polylactide. Taking 2.5 molar equivalent hydroxyl-double-terminated polylactide, 4 molar equivalent compound (a), 1 molar equivalent compound (b), 1 molar equivalent compound (c) and 36 molar equivalent triethylamine, placing the materials in a reaction container, dissolving the materials with a proper amount of dichloromethane, cooling the materials in an ice bath, slowly dropwise adding dichloromethane solution dissolved with 6 molar single amount of 1, 3, 5-benzene tricarboxychloride, stirring and reacting the mixture for 12 hours at room temperature after dropwise adding, then adding 180 wt% of polyethylene glycol oligomer, continuously stirring and mixing the mixture for 1 hour, then placing the product in a mold, and drying the product in a vacuum oven at 110 ℃ for 6 hours to obtain the oligomer swelling gel. The gel samples had good tensile toughness and resilience. When the gel is stretched or compressed, the fluorescence of the gel under 365nm ultraviolet irradiation can be changed from blue to green; the color of the alloy can be changed into orange yellow by continuously increasing the stress; the discolored gel is heated to 120 ℃ and is kept for 1.5h, and when the gel is stretched or compressed again, the fluorescence change and the discoloring property can be recovered again, and the gel shows reversible force activation characteristic. The gel material also has good self-repairing performance and shape memory function, and can be used as a multifunctional shape memory material.
Example 18
Figure BDA0001936065950002503
Carrying out ring-opening polymerization on epsilon-caprolactone at 120 ℃ for 10 hours in argon atmosphere by using a stannous octoate catalyst and triethanolamine as an initiator to prepare hydroxyl-terminated three-arm polycaprolactone; taking 0.5 molar equivalent of hydroxyl-terminated three-arm polycaprolactone, placing the hydroxyl-terminated three-arm polycaprolactone in a reaction container, dehydrating and drying the hydroxyl-terminated three-arm polycaprolactone at 120 ℃ under reduced pressure for 2h, cooling the dried hydroxyl-terminated three-arm polycaprolactone to below 60 ℃, adding 3.3 moles of single-amount dicyclohexylmethane diisocyanate and a proper amount of toluene solvent, and stirring the mixture at 80 ℃ to react for 3h to obtain an isocyanate-terminated prepolymer; and then adding 0.3 molar equivalent compound (b), 0.6 molar equivalent compound (c) and a small amount of stannous octoate catalyst into the prepolymer solution, continuously stirring and reacting for 8 hours under a nitrogen atmosphere, uniformly mixing 0.3 wt% of antioxidant 1010, 0.1 wt% of nano zinc oxide, 1 wt% of carbon fiber and a proper amount of toluene, placing the obtained material into a mold, and drying in a vacuum oven at 100 ℃ for 6 hours to obtain the polyurethane elastomer. When the elastomer is stretched, the fluorescence of the elastomer under 365nm ultraviolet illumination changes from yellow to red; when the elastomer is stretched to a large deformation, the elastomer can emit blue light, because the carbene-metal coordination bond is also stressed and activated to generate copper carbene, and the copper carbene can catalyze the chemical activation ring opening of the dioxetane to obtain indirect luminescence performance. The elastomer can be used as a stress monitoring material based on the sequential fluorescence and luminescence property changes of the elastomer.
Example 19
Figure BDA0001936065950002511
Taking 90 molar equivalent of n-butyl acrylate, 30 molar equivalent of 2-bromoethyl acrylate and 0.08 molar equivalent of AIBN, dissolving with a proper amount of tetrahydrofuran, stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere, and purifying to obtain the bromine-containing polyacrylate copolymer (a) after the reaction is finished. Pyridine is used as a catalyst, acetonitrile is used as a solvent, and a compound (b) and a compound (c) in a molar ratio of 1: 2 are stirred and reacted for 3 hours at room temperature to prepare a product I. Taking 1 molar equivalent of copolymer (a), 8 molar equivalent of product I, 10 molar equivalent of anthracene-2-yl methanol and 6 molar equivalent of compound (d), placing the materials in a reaction container, dissolving the materials with a proper amount of DMF, adding a proper amount of sodium hydroxide catalyst, stirring and reacting for 12 hours at 50 ℃ under nitrogen atmosphere, adding 5 molar equivalent of cucurbit [8] urea, uniformly mixing, placing the obtained materials in a mold, and drying for 3 hours in a vacuum oven at 100 ℃ to obtain the polymer elastomer. The elastomer has good tensile toughness, self-repairing performance and shape memory function. When the elastic body is locally pressed, the fluorescence of the pressed area under the irradiation of ultraviolet light changes from yellow green to orange red, and the fluorescence change property can be maintained for a long time, so that the elastic body can be used as an information recording and storing material.
Example 20
Figure BDA0001936065950002512
Dissolving 60 molar equivalents of polyethylene glycol monomethyl ether acrylate, 20 molar equivalents of 2-bromoethyl acrylate and 0.04 molar equivalent of AIBN with a proper amount of tetrahydrofuran, stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere, and purifying to obtain a bromine-containing polyacrylate copolymer (a) after the reaction is finished; taking 1 molar equivalent of a bromopolyacrylate copolymer (a), 8 molar equivalent of a compound (b), 5 molar equivalent of a compound (c) and 5 molar equivalent of a compound (d), placing the mixture in a reaction vessel, adding a proper amount of acetonitrile solvent, stirring and dissolving, adding a proper amount of pyridine catalyst, stirring and reacting for 10 hours at room temperature under a nitrogen atmosphere, and removing impurities and solvent after the reaction is finished to obtain crosslinked polyacrylate; in another reaction vessel, 0.8g of nanoclay particles was added to 60mL of distilled water in portions under stirring at 1000rpm, and then dispersed for 30min under stirring at 25 ℃ to obtain a suspension; then 15g of the crosslinked polyacrylate obtained above was added to the obtained suspension, and the mixture was placed in a cylindrical container and stirred at 40 ℃ for swelling for 3 hours to obtain a polymer hydrogel. The hydrogel was found to have a tensile strength of 11.5MPa and an elongation at break of 357%, and was able to undergo color and fluorescence changes when the gel was stretched or compressed. The gel material also has good self-repairing performance and shape memory function. The gel material in the embodiment can be used as a drug slow release carrier with a stress/strain indicating function.
Example 21
Figure BDA0001936065950002521
The preparation method comprises the steps of taking 3.5 molar equivalent poly (1, 6-hexanediol) polyester diol (molecular weight is 1500), placing the poly (1, 6-hexanediol) polyester diol in a reaction container, carrying out reduced pressure dehydration drying at 120 ℃ for 2 hours, cooling to below 60 ℃, adding 0.75 molar single amount of compound (a), 0.25 molar equivalent compound (b), 5 drops of stannous octoate and a proper amount of toluene solvent, uniformly mixing, adding 3.05 molar single amount of triphenylmethane triisocyanate, stirring at 60 ℃ under nitrogen atmosphere for reaction for 16 hours, and placing the product in a vacuum oven for drying to obtain the polymer elastomer. The elastomer sample has good tensile toughness, under low tensile strain, the elastomer can emit blue light, and along with the increase of tensile deformation, the elastomer can emit green light, because under low tensile strain, the carbene-metal coordination bond in the elastomer can be stressed and activated to generate carbene, and the carbene-metal coordination bond can catalyze the chemical ring opening of the dioxetane in the side group to generate blue light; under the action of higher tensile force, the cinnamic acid dimer in the compound can be stressed and activated to generate a conjugated electron-withdrawing group, and the dioxetane is converted into green light through an energy transfer process, so that the luminescent property related to stress/strain is shown. Based on the properties, the elastomer material can be used as a stress/strain warning material, and is particularly suitable for stress/strain monitoring application scenes with poor light.
Example 22
Figure BDA0001936065950002522
Reacting a compound (a) and a compound (b) with excessive methacryloyl chloride respectively by using triethylamine as a catalyst and dichloromethane as a solvent to prepare a dimethacrylate cross-linking agent I and a cross-linking agent II; taking 120 molar equivalent of methacryloyl ethyl sulfobetaine, 10 molar equivalent of a cross-linking agent I, 5 molar equivalent of a cross-linking agent II and 0.1 molar equivalent of 2-oxoglutaric acid, dissolving the materials in a proper amount of deionized water, placing the obtained reactant solution in a glass mold, introducing nitrogen, bubbling, deoxidizing for 30min, then irradiating for 5h under ultraviolet light at 20 ℃, after the reaction is finished, placing the obtained gel in deionized water for 24h, replacing water every 6h to remove non-cross-linked components, and obtaining the polymer hydrogel after water absorption, swelling and balancing. The tensile strength of the resulting hydrogel was measured to be 6.95MPa, and the elongation at break was 275%. When the gel is slowly stretched, NO can be slowly released; the gel can not release NO again when the stretching is stopped, thereby showing a force-induced controllable NO release process; when the gel is rapidly stretched to a large deformation, a large amount of NO can be rapidly released, and high-intensity blue fluorescence can be emitted, so that the NO is fed back to be basically and completely released. The gel material in the embodiment can be used as a slow release carrier or a biomedical device with a force-induced controllable NO release function, the process of releasing NO can be well regulated and controlled through mechanical force, long-acting and lasting curative effect is obtained, and a user can conveniently replace and maintain the gel material based on the fluorescence property change of the gel material.
Example 23
Figure BDA0001936065950002523
Taking dichloromethane as a solvent, triethylamine as a catalyst, carrying out stirring reaction on four-arm polyethylene glycol (with the molecular weight of 5000) and excessive succinic anhydride for 4 hours at room temperature, then carrying out reflux reaction for 30 minutes to obtain carboxyl-terminated four-arm polyethylene glycol, taking dichloromethane as a solvent, carrying out reaction on the dichloromethane and excessive thionyl chloride for 1.5 hours at room temperature under a nitrogen atmosphere to obtain acyl chloride-terminated four-arm polyethylene glycol, taking 2 molar equivalents of acyl chloride-terminated four-arm polyethylene glycol, 1 molar equivalent of a compound (a), 3 molar equivalents of a compound (b) and 0.5 molar equivalent of a compound (c), placing the materials into a reaction vessel, counting the total mass of 100 parts, dissolving the materials by using a proper amount of tetrahydrofuran, adding 16 molar equivalents of a pyridine catalyst, carrying out stirring reaction for 12 hours at room temperature, adding 160 parts of polyethylene glycol oligomer, stirring and mixing for 1 hour, then drying for 24 hours in a vacuum oven, obtaining an oligomer swelling gel after the tetrahydrofuran volatilizes completely, and when a gel sample is compressed, the gel rapidly increases the force along with the increase of compression deformation, because the activation of azo groups under the action of the stress, the generated by the action of promoting the free radical of a nitrile group, the acrylonitrile-terminated monomer, the acrylonitrile-terminated four-terminated polyethylene glycol-terminated four-arm polyethylene glycol-terminated four.
Example 24
Figure BDA0001936065950002531
Taking 2 molar equivalents of acyl chloride-terminated four-arm polyethylene glycol, 1.5 molar equivalents of the compound (a), 2 molar equivalents of the compound (b) and 1.5 molar equivalents of the compound (c), placing the materials into a reaction vessel, taking the total mass of the materials as 100 parts, dissolving the materials by using a proper amount of tetrahydrofuran, adding 16 molar equivalents of a pyridine catalyst, stirring and reacting for 12 hours at room temperature, placing the obtained product into deionized water for 24 hours, changing water every 6 hours to remove non-crosslinking components, and then placing the product into a large amount of aqueous solution of purple litmus to achieve water absorption swelling balance to obtain the polymer hydrogel. The polymer has low glass transition temperature and hydrogen bonding effect of side groups, and thus has the features of soft texture, tear resistance, wide extensibility, etc. When the gel sample is locally compressed, the gel sample can generate a sequential local color gradual change process along with the increase of the compressive stress, and the gel sample can be used as a toy material or an anti-counterfeiting material with a force-induced color change function.
Example 25
Figure BDA0001936065950002532
Taking 12 molar equivalents of amino-di-terminated polyethylene glycol (molecular weight is 800), 0.25 molar equivalent of series-connection composite force sensitive group compound (a), 2.5 molar equivalents of tethered composite force sensitive group compound (b) and 4.5 molar equivalents of ethylenediamine tetraacetic acid, placing the materials in a reaction vessel, dissolving with a proper amount of DMF, then adding 36 molar equivalents of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 24 molar equivalents of 4-dimethylaminopyridine, stirring at room temperature for 24 hours, then adding 210 wt% of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ionic liquid, 10 wt% of dicyclopentadiene, 2 wt% of tributyl phosphite and 5 wt% of graphene, stirring and mixing for 30 minutes, placing the mixed material in a mold, drying in a vacuum oven at 60 ℃ for 24 hours, an ionic liquid swollen gel with high electrical conductivity and high thermal conductivity can be obtained. When the gel is compressed to a certain deformation amount, the gel can turn into red, because the tandem composite force sensitive groups in the gel are firstly stressed and activated to generate color change; when the stretching is continued, the tethered composite force sensitive group can be stressed and activated to obtain the force-induced toughening effect, and the good structural stability can be provided based on the non-chain-breaking force activation characteristic of the force sensitive group. In addition, the tethered composite force sensitive group can generate a ruthenium carbene group with a catalytic effect after being stressed and activated, but the catalytic inhibitor tributyl phosphite is dispersed in the tethered composite force sensitive group, so that the tethered composite force sensitive group can not immediately catalyze and disperse dicyclopentadiene in a polymer matrix for ring-opening polymerization, the stress or failure process of the material can be conveniently analyzed, and when the gel is locally heated to 145 ℃, the ruthenium carbene catalyst can rapidly catalyze dicyclopentadiene for ring-opening polymerization to obtain further crosslinking, so that the material is repaired and the mechanical strength is improved, and the tethered composite force sensitive group has good practicability. Based on the rich properties, the gel can be used as a multifunctional sealing material.
Example 26
Figure BDA0001936065950002533
Reacting a compound (a) and a compound (b) with excessive acryloyl chloride by using triethylamine as a catalyst and dichloromethane as a solvent to prepare a diacrylate cross-linking agent I and a cross-linking agent II. Dissolving sodium alginate (LFR5/60 and LF20/40) and acrylamide in distilled water, wherein the mass concentration of the sodium alginate and the mass concentration of the acrylamide are respectively 5 wt% and 20 wt%, and stirring for 48h at room temperature to obtain a clear solution; and adding a proper amount of a cross-linking agent I and a cross-linking agent II, tetramethyl ethylene diamine, calcium sulfate and ammonium persulfate into the solution, wherein the weight of the cross-linking agent I, the weight of the cross-linking agent II, the weight of the tetramethyl ethylene diamine, the weight of the calcium sulfate and the weight of the ammonium persulfate are respectively 0.8 percent, 0.6 percent, 1.8 percent and 0.6 percent of that of acrylamide, adding the obtained materials into a glass reaction container, introducing nitrogen, bubbling, deoxidizing, then carrying out ultraviolet irradiation reaction for 15min under nitrogen atmosphere at 365nm, and standing for reaction for 12h after the irradiation is stopped, thus obtaining the polymer hydrogel. Under the action of mechanical force, the o-phthalaldehyde series covalent single force sensitive groups and the light-operated DA series covalent single force sensitive groups can be activated by force to cause polymer chains to break, so that the de-crosslinking effect is obtained; under the irradiation of ultraviolet light, the light-controlled DA force sensitive group structure is locked, so that the force sensitive group structure can not be activated, and a stable crosslinking effect is obtained. The gel sample also has the characteristics of toughness, skin friendliness, low biotoxicity, good adhesion and the like, and can be used as a degradable medical adhesive material with dual control of mechanical force and ultraviolet light.
Example 27
Figure BDA0001936065950002541
The compound I is prepared by the reaction of the compound (a) and excessive 1, 3, 5-benzene trimethyl chloride by taking triethylamine as a catalyst and dichloromethane as a solvent. The modified polybutadiene is prepared by esterification reaction of hydroxyl-terminated polybutadiene (b) and an excessive compound (c) by taking dicyclohexylcarbodiimide and 4-dimethylaminopyridine as a catalytic system and tetrahydrofuran as a solvent. Taking 0.6 molar equivalent modified polybutadiene, 0.4 molar equivalent compound I, 6 molar equivalent compound (d), 3 molar equivalent compound (e) and 3 wt% benzoin dimethyl ether, dissolving with appropriate amount of chloroform, placing the obtained solution in a glass mold, introducing nitrogen gas, bubbling, deoxidizing for 30min, and then, under nitrogen atmosphere, carrying out 365nm ultraviolet illumination reaction for 3h to obtain the polybutadiene elastomer. The elastomer can change color under the action of stretching or compression, and the stress on the material can be visually fed back. Based on the reversible characteristics of light-operated DA force-sensitive group crosslinking and end group hydrogen bond crosslinking, the elastomer has good tensile toughness, self-repairing performance and shape memory function. Under the ultraviolet irradiation, the structure of the light-control DA force-sensitive group in the material is locked and cannot be activated by force, the ductility of the polymer material is reduced, the thermal stability and the dimensional stability are obviously improved, and the material can be used as a plugging material with dual responses of mechanical force and ultraviolet light.
Example 28
Figure BDA0001936065950002542
Taking 0.4 molar equivalent of side group vinyl polysiloxane copolymer (a) (wherein the vinyl content is 12 percent), 4.5 molar equivalent of compound (b), 2.5 molar equivalent of compound (c), 15 molar equivalent of 4-cyano-1-butyl mercaptan, 15 molar equivalent of 1-butyl-4- (2-mercaptoethoxy) pyridine-1-ammonium chloride and 5wt percent benzoin dimethyl ether, placing the mixture in a reaction vessel, dissolving the mixture by using a proper amount of chloroform, introducing nitrogen, bubbling, deoxidizing for 30min, then carrying out a reaction under the nitrogen atmosphere and 365nm ultraviolet irradiation for 30min, and removing the solvent after the reaction is finished to obtain the polymer elastomer. When the elastomer is stretched at a low stretching rate, the deformation area gradually becomes red, and the stress-strain curve fluctuates to show that the strength is increased, because the force sensitive groups in the elastomer are stressed and activated at the low stretching rate, the generated active groups can react with cyano-group side groups to obtain the force-induced crosslinking effect, and the mechanical strength is improved. When the material cracks, the ion-dipole effect in the material can also provide certain self-repairing performance. When the tensile stress of the elastomer is gradually increased, the gated composite force sensitive group can be activated step by step to obtain a force-induced toughening effect, and chain breakage can not occur after complete force-induced activation, so that good structural stability can be obtained. The elastomer material in the present embodiment is suitably used as a highly reliable sealing material.
Example 29
Figure BDA0001936065950002551
The modified polyethylene is prepared by carrying out melt grafting modification on low molecular weight polyethylene by taking dicumyl peroxide as an initiator and maleic anhydride as a grafting modifier, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 15. 40g of graft modified polyethylene and 80mg of antioxidant 168 are placed in a reaction vessel, heated to 165 ℃ under nitrogen atmosphere, stirred and melted, and then 2.1g of compound (a), 0.65g of compound (b), 0.4g of 1, 8-octanediol, 1.2g of compound (c), 1.4g of p-toluenesulfonic acid, 4g of dibutyl phthalate, 1.2g of carbon fibers and 0.7g of Tb (NO)3)3And 0.5g of dimethyl silicone oil, continuously stirring and reacting for 4 hours, then placing the product into a mold, carrying out compression molding at 120 ℃, and then slowly cooling to room temperature to obtain the fiber reinforced hard polymer solid. Applying stress to the sample to bend the sample, wherein the sample can emit green fluorescence under low bending strain; when the deformation is further increased, the color of the material becomes orange yellow. The hydrogen bonding in the cross-linked network can improve the tear resistance of the material. The true bookIn embodiments, the solid material may be used as a polymer sheet or a mechanical part having a deformation detecting function.
Example 30
Figure BDA0001936065950002552
Putting 5 molar equivalent polytetrahydrofuran diol (molecular weight is 3000) into a reaction container, dissolving with proper amount of toluene, adding 13 molar equivalent hexamethylene diisocyanate, uniformly mixing, adding a small amount of stannous octoate catalyst, stirring at 70 ℃ for reaction for 2 hours under nitrogen atmosphere, adding 4 molar equivalent triethanolamine, 1 molar equivalent compound (a), 1 molar equivalent compound (b) and 4 molar equivalent N-acetyl-L-cysteine, continuing to react for 8 hours, then putting the reaction solution into a mold, and carrying out heat preservation and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the polyurethane elastomer. The elastomer has good tensile toughness, tear resistance and cohesiveness. When the elastic body is slowly stretched, the color of the deformation area is changed into light yellow, the stretching is stopped, and the yellow color is faded; the color can be changed when the stretching is continued; when the elastomer is stretched to a larger deformation amount, the two force sensitive groups can be activated under the stress, and the active groups generated by the force activation can also generate further chemical reaction, so that a certain force-induced enhancement effect can be obtained. The elastomer material can be used as a bonding material with self-repairing performance and force-induced enhancement function.
Example 31
Figure BDA0001936065950002553
Taking 2 molar equivalent hydroxyl-terminated polybutadiene-acrylonitrile, 0.25 molar equivalent compound (b) and 0.25 molar equivalent compound (c), placing the materials in a reaction container, recording the total mass of the materials as 100 parts, adding 1.8 parts of deionized water, 25 parts of monofluoroethane, 6 parts of foam homogenizing agent AK8803 and 1.7 parts of N, N-dimethylcyclohexylamine, stirring at a high speed and mixing uniformly, adding polyphenyl polymethylene polyisocyanate, wherein the isocyanate index is 1.05, quickly stirring for 15 seconds, immediately pouring the mixture into a mold for foaming, solidifying at normal temperature for 15 minutes, taking out the foam, and curing at room temperature for 7 days to obtain the polyurethane rigid foam. When the foam sample is stretched, the foam sample can emit yellow light, the color of the foam sample can gradually become orange red when the foam sample is further stretched, the sequential light emission and color change can well feed back the stress magnitude of the material, and the foam sample can be coated on the surfaces of the supporting frame and the cable rope to play a stress warning function.
Example 32
Figure BDA0001936065950002561
6 molar equivalents of polyoxypropylene diamine 2000 and 1.5 molar equivalents of a single amount of compound (a) are taken and placed in a reaction vessel, a proper amount of dimethylbenzene is used for dissolving, 5 molar equivalents of toluene diisocyanate and a small amount of dibutyltin dilaurate are added, then the reaction is carried out for 1 hour under nitrogen atmosphere at 60 ℃, 0.5 molar equivalent of a single amount of compound (b) and 2 molar equivalents of triphenylmethane triisocyanate are added, the reaction is continued for 8 hours, and after the reaction is finished, the polymer organogel can be obtained. When the gel is slightly pressed locally, the coumarin dimer in the pressed area is stressed and activated to generate a fluorescent coumarin derivative, but the ibuprofen drug molecules cannot be released; further increasing the pressing stress, the gel can emit blue light and can release ibuprofen drug molecules, so as to obtain the effects of analgesia and anti-inflammation. The release rate of drug molecules can be well regulated and controlled by controlling the pressing action strength, and the hydrogel material can be used as a medical gel material with a force-induced controllable drug release function.
Example 33
Figure BDA0001936065950002562
Taking 0.5 molar equivalent of methyl hydrogen siloxane-dimethyl siloxane copolymer (molecular weight is 20000), 1 molar equivalent of compound (a), 1 molar equivalent of compound (b), 7 molar equivalent of 1, 4-butanediol vinyl ether and 6 molar equivalent of alkenyl single-ended crystalline polypropylene (molecular weight is 3000), putting the mixture into a reaction vessel, adding a proper amount of cyclohexanone solvent, uniformly mixing, adding a proper amount of chloroplatinic acid catalyst, stirring and reacting for 4 hours at 90 ℃ under a nitrogen atmosphere, and removing impurities and solvent after the reaction is finished to obtain the polysiloxane elastomer. Two composite force sensitive groups can generate force-induced color change and force-induced toughening effects after being subjected to force activation under the action of mechanical force, and can be used as a stress warning material.
Example 34
Figure BDA0001936065950002563
Dissolving 80 mol equivalent of styrene, 0.1 mol equivalent of methyl 2-bromopropionate and 1 mol equivalent of pentamethyldiethylenetriamine with a proper amount of tetrahydrofuran, introducing nitrogen, bubbling, deoxidizing for 30min, adding 1 mol equivalent of cuprous bromide, stirring and reacting for 48h at 80 ℃ in an argon atmosphere, and purifying to obtain bromine single-terminated polystyrene after the reaction is finished; dissolving 3 molar equivalents of bromine mono-terminated polystyrene and 1 molar equivalent of hydroxyl di-terminated polybutadiene in a proper amount of dimethyl sulfoxide, adding 15 molar equivalents of sodium hydroxide, stirring at room temperature for reaction for 24 hours, and purifying to obtain a triblock copolymer after the reaction is finished; and then taking 0.5 molar equivalent of the triblock copolymer, 6 molar equivalent of the compound (a), 2 molar equivalent of the compound (b) and 0.1 molar equivalent of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, putting the three-block copolymer, the 2 molar equivalent of the compound (b) and the 0.1 molar equivalent of the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide into a glass reaction vessel, adding a proper amount of dimethyl sulfoxide to dissolve the three-block copolymer, uniformly mixing the two components, carrying out ultraviolet illumination reaction for 3 hours under a nitrogen atmosphere, and removing impurities and solvents after the reaction. When the elastomer is compressed, the five-membered ring force sensitive group is stressed and activated to generate color change; with further increase in pressure, the bending activated force sensitive groups therein can also be activated and catalyze the chemiluminescence of the dioxetane group through a self-elimination reaction. The elastomer material can be used as a stress monitoring material with color and luminous warning functions, and is particularly suitable for stress monitoring scenes with poor illumination.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (6)

1. A force-responsive polymer having a monohybrid network structure, comprising only one crosslinked network and comprising both covalent and non-covalent crosslinks having non-dynamic covalent linkages with a degree of crosslinking above the gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
2. The force-responsive polymer of claim 1, wherein the force-responsive polymer has one of the following structures:
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two force sensitive groups;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two covalent single force sensitive groups;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network comprises at least one covalent single force sensitive group and at least one non-covalent single force sensitive group;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least one covalent single force sensitive group and at least one composite force sensitive group;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two non-covalent single force sensitive groups;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least one non-covalent single force sensitive group and at least one composite force sensitive group;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two composite force sensitive groups;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a covalent single force sensitive group with dynamic covalent characteristics;
the force-responsive polymer only contains a crosslinking network, wherein the crosslinking network contains common covalent crosslinking and non-covalent crosslinking at the same time, the crosslinking degree of the common covalent crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point; the cross-linked network contains at least two covalent single-force sensitive groups, and the covalent single-force sensitive groups are covalent single-force sensitive groups with dynamic covalent characteristics;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a non-chain-breaking covalent single force sensitive group; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least two covalent single force sensitive groups, and at least one covalent single force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the crosslinking network contains at least one non-chain-breaking covalent single force sensitive group and at least one covalent single force sensitive group with dynamic covalent characteristics; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the crosslinking network contains at least one non-chain-breaking covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least one non-chain-breaking covalent single force sensitive group and at least one composite force sensitive group; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least two covalent single-force sensitive groups, and the covalent single-force sensitive groups are non-chain-breaking covalent single-force sensitive groups; wherein, the sum of the crosslinking degrees of the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least two force sensitive groups, and at least one of the force sensitive groups is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the crosslinking network contains at least two covalent single force sensitive groups, at least one of which is a covalent single force sensitive group with a chain-breaking non-dynamic covalent characteristic; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one dynamic covalent characteristic covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single-force sensitive group and at least one non-covalent single-force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least one chain-broken non-dynamic covalent characteristic covalent single force sensitive group and at least one compound force sensitive group; wherein, the crosslinking degree of the covalent single force sensitive group crosslinking with the chain-breaking type non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least two covalent single force sensitive groups, and the covalent single force sensitive groups are all covalent single force sensitive groups with chain-breaking type non-dynamic covalent characteristics; wherein, the sum of the crosslinking degrees of the covalent single force sensitive group crosslinking with the chain-breaking non-dynamic covalent characteristic is above the gel point, and the crosslinking degree of the non-covalent crosslinking is above or below the gel point;
the force-responsive polymer contains only one cross-linked network, wherein only the force-sensitive group cross-links and the non-covalent cross-links are contained; the cross-linked network contains at least one force sensitive group which is a non-chain-breaking covalent single force sensitive group and at least one chain-breaking covalent single force sensitive group with non-dynamic covalent characteristics; wherein, the crosslinking degree of the non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, the crosslinking degree of the chain-breaking covalent non-dynamic covalent characteristic covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the two is above the gel point; wherein the degree of non-covalent cross-linking is above or below the gel point;
the force-responsive polymer only contains a cross-linked network, wherein common covalent bond covalent cross-linking, force-sensitive group cross-linking and non-covalent cross-linking are simultaneously contained; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a non-chain-breaking covalent single force sensitive group; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of non-chain-breaking covalent single-force sensitive group crosslinking is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the non-chain-breaking covalent single-force sensitive group crosslinking is above the gel point; wherein the degree of non-covalent cross-linking is above or below the gel point;
the force-responsive polymer only contains a cross-linked network, wherein common covalent bond covalent cross-linking, force-sensitive group cross-linking and non-covalent cross-linking are simultaneously contained; the cross-linked network contains at least two force sensitive groups, and at least one force sensitive group is a covalent single force sensitive group with chain-breaking type non-dynamic covalent characteristics; wherein, the crosslinking degree of common covalent crosslinking is below the gel point, the crosslinking degree of the covalent single force sensitive group crosslinking with the broken chain type non-dynamic covalent characteristic is below the gel point, but the sum of the crosslinking degrees of the common covalent crosslinking and the broken chain type non-dynamic covalent characteristic is above the gel point; wherein the degree of non-covalent crosslinking is above or below the gel point.
3. The force-responsive polymer with a single-hetero network structure according to claim 1, wherein the force-responsive polymer formulation further comprises any one or more of the following additives or utilizable substances: auxiliary agent, filler and swelling agent.
4. The force-responsive polymer with a monohybrid network structure according to claim 1, wherein the form of the force-responsive polymer is any one of the following: common solids, gels, elastomers, foams.
5. The force-responsive polymer with a single-hetero network structure according to any one of claims 1 to 4, wherein the force-responsive polymer is applied to the following materials or articles: stress induction materials, self-repairing materials, toughness materials, shape memory materials, toy materials, functional coating materials, intelligent sensors, bonding materials and plugging materials.
6. A method for realizing force-induced response, which is characterized in that a force-induced responsive polymer with a single-hetero network structure is provided, wherein only one crosslinking network is contained, and non-dynamic covalent crosslinking and non-covalent crosslinking are contained simultaneously, and the crosslinking degree of the non-dynamic covalent crosslinking is higher than the gel point; wherein the cross-linked network contains at least two force sensitive groups; under the action of mechanical force, the force sensitive groups in the material undergo chemical and/or physical changes to realize force-induced response.
CN201910010078.4A 2019-01-01 2019-01-01 Force-induced responsive polymer with single-hybrid network structure Pending CN111378181A (en)

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