CN111378163A

CN111378163A - Combined hybrid dynamic polymer and application thereof

Info

Publication number: CN111378163A
Application number: CN201910000079.0A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Xiaoyang Sports Technology Co ltd
Priority date: 2019-01-01
Filing date: 2019-01-01
Publication date: 2020-07-07

Abstract

The invention discloses a composite hybrid dynamic polymer, which contains at least two types of dynamic covalent bonds and optional hydrogen bonds. The dynamic polymer material with wide controllable range, rich structure and various performances can be prepared by introducing dynamic covalent bonds and hydrogen bonds with different dynamic responsivities into the combined hybrid dynamic polymer. By utilizing the differences among different dynamic covalent bonds and hydrogen bonds, the combined hybrid dynamic polymer can show a hierarchical dynamic reversible effect under different conditions, thereby showing the performances of self-repairability, reusability, stimulus responsiveness and the like. The dynamic polymer can be widely applied as a self-repairing material, a tough material, a sealing material, an interlayer adhesive and the like.

Description

Combined hybrid dynamic polymer and application thereof

Technical Field

The invention relates to the field of intelligent materials, in particular to a combined hybrid dynamic polymer formed by at least two types of dynamic covalent bonds and optional hydrogen bonds.

Background

The intelligent material, which can be called as sensitive material or stimulus response material, is a new material which can sense, diagnose and respond to external stimulus and has function execution capacity, which blurs the boundary between the traditional structural material and the functional material and realizes the functionalization, intellectualization and diversification of the structure. Due to the connotation and characteristics of the intelligent material, the intelligent material rapidly arouses the interests of a large number of scientists, develops into a fourth-generation material following natural materials, synthetic polymer materials and artificial design materials, is widely applied to the military and civil fields of buildings, aerospace, medical treatment and the like, and is one of the important development directions of the technical development of modern high and new materials.

Traditional polymer materials mainly maintain the shape and the molecular structure thereof through covalent bonds, and because the covalent bonds have high bonding energy and the chain structure is stable and difficult to change, the materials are usually not reconfigurable, recyclable and reprocessable, and the application of the materials in various fields is limited. By introducing the dynamic reversible covalent bond into the polymer, the method is a feasible method for forming a novel intelligent polymer, and can effectively expand the application field of materials. Such dynamic covalent bonds can be sensitive to temperature changes, light, radiation or other external conditions, and through reversible addition/condensation or reversible bond exchange mechanisms, the chain structure of the polymer can be changed and reconfigured. Compared with common covalent bonds, the dynamic covalent bonds can embody the dynamic reversibility in supermolecule chemistry, have the functions of 'proofreading' and 'error correction' like supermolecule interaction, can obviously influence the dynamic covalent chemical balance by changing external conditions, and further enable the polymer to embody self-repairability, recoverability, stimulus responsiveness and bionic mechanical properties, and compared with supermolecule acting force, the polymer has stronger bond energy, smaller influence of thermal mechanics and more stable properties.

With further expansion and deepening of research, the variety of dynamic covalent bonds is more and more abundant, but the research on dynamic polymers at present basically stays in a single dynamic covalent bond system, and due to the limited dynamic effect and dynamic regulation and control capability of the single dynamic covalent bond, the single dynamic covalent bond is difficult to have the synergistic and orthogonal comprehensive performance, and in order to obtain the dynamic polymers with diversity and synergistic and orthogonal dynamics, a novel combined hybrid dynamic polymer needs to be developed to solve the problem.

Disclosure of Invention

The present invention addresses the above background by providing a combinatorial hybrid dynamic polymer comprising at least two types of dynamic covalent bonds and optionally hydrogen bonds. The combined hybrid dynamic polymer has an orthogonal/synergistic dynamic reversible effect, and can embody self-repairability, recoverability, stimulus responsiveness and bionic mechanical properties.

The invention is realized by the following technical scheme:

the invention provides a combined hybrid dynamic polymer, which contains at least two crosslinking networks, wherein the crosslinking networks contain at least two types of dynamic covalent bonds and optional hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

According to a preferred embodiment of the invention, the combined hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least two types of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinked network contains at least one hydrogen bond and the degree of crosslinking of the hydrogen bond crosslinks is above its gel point.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bond and hydrogen bond, and the cross-linking degree of the two cross-links is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer has a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one type of dynamic covalent bond, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer has a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one hydrogen bond, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types.

In the above preferred embodiment, a supramolecular polymer having a supramolecular crosslinking degree below its gel point and/or supramolecular polymer particles having a supramolecular crosslinking degree above its gel point may also be dispersed in the provided combinatorial hybrid dynamic polymer crosslinked network.

The invention also provides a combined hybrid dynamic polymer, which only contains a cross-linked network, and at least two types of dynamic covalent bonds and optional hydrogen bonds are contained in the cross-linked network; wherein the dynamic covalent bond is selected from the group consisting of a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a combinable exchangeable acyl bond, a dynamic covalent bond induced based on steric effects, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of undergoing an alkene cross-metathesis reaction, an unsaturated carbon-carbon triple bond capable of undergoing an alkyne cross-metathesis reaction, an amine alkene-michael addition dynamic covalent bond, a triazolinedione-indole based dynamic covalent bond, a dinitrohetero carbene based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a combination of dynamic exchangeable trialkyl sulfonium bonds; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

The invention provides a combined hybrid dynamic polymer, which only contains a cross-linked network, wherein the cross-linked network contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the hydrogen bond is formed by taking carbamate, carbamide, thiocarbamate, thiourea, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin and derivatives of the above groups as hydrogen bond groups; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

According to a preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the crosslinking degree of the dynamic covalent bond crosslinking is below the gel point, the crosslinking degree of the hydrogen bond crosslinking is below the gel point, and the sum of the crosslinking degrees of the two is above the gel point.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the degree of crosslinking by dynamic covalent bond crosslinking is below the gel point and the degree of crosslinking by hydrogen bond crosslinking is above the gel point.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the degree of crosslinking by dynamic covalent bond crosslinking is above the gel point and the degree of crosslinking by hydrogen bond crosslinking is below the gel point.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point.

In the preferred embodiment, the supramolecular polymer having a supramolecular crosslinking degree below the gel point and/or supramolecular polymer particles having a supramolecular crosslinking degree above the gel point may be dispersed in the hybrid dynamic polymer crosslinked network.

The invention provides a combined hybrid dynamic polymer which is a non-crosslinked structure and contains at least two types of dynamic covalent bonds and optional hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic selenazon bond, a dynamic covalent bond based on reversible free radicals, a combinable exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis reaction, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis reaction, an amine-Michael addition dynamic covalent bond, a dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on dinitrohetero-carbene, a hexahydrotriazine dynamic covalent bond, and a combination of dynamic exchangeable trialkyl sulfonium bonds; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

The invention provides a combined hybrid dynamic polymer which is a non-crosslinked structure and contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein, the hydrogen bond is formed by carbamido, thiocarbamate, thiourea, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin and derivatives of the above groups as hydrogen bond groups; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

The invention provides a combined hybrid dynamic polymer which is a non-crosslinked structure and contains at least two types of dynamic covalent bonds and hydrogen bonds formed by side hydrogen bond groups; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

In addition, the present invention can also have other various dynamic polymer structure embodiments, one embodiment can comprise a plurality of same or different non-crosslinked polymer chains and/or crosslinked polymer networks, and the same crosslinked network can comprise different dynamic covalent crosslinks and/or different hydrogen bond crosslinks, wherein the hydrogen bond can be in the same crosslinked network with the dynamic covalent crosslinks or in each independent crosslinked network or partially interact with the dynamic covalent crosslinked network, and can also be dispersed in the dynamic covalent crosslinked network in the form of a non-crosslinked polymer.

In an embodiment of the present invention, the dynamic covalent bond is preferably selected from one of the following combinations:

combination 1: at least two of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a triazolinedione-indole based dynamic covalent linkage, an aminoalkene-michael addition dynamic covalent linkage, a dinitroheterocarbene based dynamic covalent linkage, a dynamic exchangeable trialkylsulfonium linkage combination;

and (3) combination 2: at least two of dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, and amine alkene-Michael addition dynamic covalent bond combinations;

and (3) combination: at least two of dynamic siloxane bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross-metathesis reactions, unsaturated carbon-carbon triple bonds that can undergo alkyne cross-metathesis reactions, [2+2] cycloaddition dynamic covalent bonds, [2+4] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-michael addition dynamic covalent bonds, and combinations of dynamic covalent bonds based on triazolinedione-indole.

Combinations of dynamic covalent bonds included in the hybrid dynamic polymers provided in the present invention include, but are not limited to, the preferences set forth above, and can be reasonably combined and selected by one skilled in the art according to specific practical needs.

In an embodiment of the present invention, the linking group for linking the dynamic covalent bond and/or the hydrogen bonding group may be any one or more selected from a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue, a divalent or polyvalent inorganic small molecule chain residue, and a divalent or polyvalent inorganic large molecule chain residue.

In embodiments of the present invention, the hybrid dynamic polymer and its raw material components may or may not have one or more glass transition temperatures. At least one of them is below 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or above 100 ℃ for the glass transition temperature of the composite hybrid dynamic polymer.

In embodiments of the invention, the combinatorial hybrid dynamic polymers and their compositions and polymer chain topologies in the feedstock components can be selected from linear, cyclic, branched, clustered, crosslinked, and combinations thereof.

In the embodiment of the invention, the form of the combined hybrid dynamic polymer can be solution, emulsion, paste, gum, common solid, elastomer, gel (including hydrogel, organic gel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), foam material and the like.

During the preparation process of the combined hybrid dynamic polymer, certain solvent, other auxiliary agents/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.

In an embodiment of the invention, the combinatorial hybrid dynamic polymer is applicable to the following materials or articles: self-repairing coating, self-repairing sheet material, self-repairing binder, sealing material, toughness material, energy storage device material, interlayer adhesive, toy and shape memory material.

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

(1) the combined hybrid dynamic polymer comprises at least two types of dynamic covalent bonds and optional hydrogen bonds, makes full use of the dynamic differences between the dynamic covalent bonds and the hydrogen bonds, exerts orthogonality and cooperativity effects, and obtains the dynamic polymer with self-repairing, recoverable and reusable characteristics; at the same time, polymeric materials also exhibit good processability and are easy to recycle and reuse, which is difficult to achieve in existing polymeric systems. In addition, different dynamic covalent bonds are selected, so that the dynamic polymer can keep a balanced structure under specific conditions, can show different response effects to external stimuli such as heat, illumination, pH, oxidation reduction and the like, and can promote or slow down dynamic reversible balance under proper environment by selectively controlling the external conditions, so that the dynamic polymer is in a required state. By combining the hydrogen bonds with the dynamic covalent bonds, the prepared dynamic polymer material can have a certain balance structure and mechanical strength under specific conditions, the dynamic property is provided by the hydrogen bonds only, and the dynamic covalent bonds can show dynamic reversibility under other specific conditions, so that the material can be completely self-repaired, recycled and plastically deformed. The combined hybrid dynamic polymer can show multiple response effects and selective responsiveness, which is difficult to achieve in the existing supermolecular chemistry and dynamic covalent system. Meanwhile, because the common covalent crosslinking above the gel point is not available, the dynamic polymer material can realize self-repairing, shaping, recycling and reprocessing to a greater extent, so that the polymer material has a wider application range and a longer service life.

(2) The combined hybrid dynamic polymer in the invention can show good controllability. By controlling parameters such as molecular structure, functional group number, molecular weight and the like of the compound serving as the raw material, the dynamic polymer with different topological structures, apparent characteristics, adjustable performance and wide application can be prepared. Based on the difference of the dynamic properties of hydrogen bonds and different types of dynamic covalent bonds, the polymer material with richer structure, more diverse performance and more hierarchical dynamic reversible effect can be obtained, so that the method has outstanding advantages.

(3) Different dynamic covalent bonds and hydrogen bonds contained in the combined hybrid dynamic polymer can generate dynamic equilibrium reaction under specific conditions to perform bond dissociation and re-bonding, self-repairing and recycling are realized, and good durability and reusability are reflected, which is an effect that other polymer materials are difficult to achieve. The existence of different dynamic covalent bonds with different strengths and dynamic properties and hydrogen bonds enables the combined hybrid dynamic polymer in the invention to embody multiple dynamic properties and responsiveness.

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

According to a preferred embodiment of the invention, the combined hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types. In the embodiment, the dissociation of one type of dynamic covalent bonds does not immediately cause the failure of the other type of dynamic covalent cross-linked network, and the structure and the performance of one dynamic covalent cross-linked network can be respectively regulated and controlled by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, so that the aim of reasonably regulating and controlling the performance of the dynamic polymer is fulfilled.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least two types of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinked network contains at least one hydrogen bond and the degree of crosslinking of the hydrogen bond crosslinks is above its gel point. In this embodiment, the introduction of the hydrogen bond crosslinked network can produce synergistic and orthogonal effects, which is beneficial to improve the tolerance of the material.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bond and hydrogen bond, and the cross-linking degree of the two cross-links is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types. In the embodiment, by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, the performances of the covalent bonds and hydrogen bonds in different dynamic covalent cross-linked networks can be fully exerted, and outstanding orthogonality and cooperativity are obtained.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer has a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one type of dynamic covalent bond, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types. In this embodiment, three dynamic covalent cross-linked networks exist independently of each other, and each network may also be independent of each other in raw material composition, so that the dynamic polymer exhibits different orthogonality and cooperativity by virtue of the differences in dynamics and stability between the different cross-linked networks.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer has a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and the degree of cross-linking of the dynamic covalent bonds is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one hydrogen bond, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types. In this embodiment, the dynamic covalent cross-linked network and the hydrogen bond cross-linked network exist independently, and the networks can also be independent from each other in raw material composition, so that the dynamic polymer can show different orthogonality and cooperativity by utilizing the difference of dynamic property and stability between different cross-linked networks.

In the above preferred embodiment, a supramolecular polymer having a supramolecular crosslinking degree below its gel point and/or supramolecular polymer particles having a supramolecular crosslinking degree above its gel point may also be dispersed in the provided combinatorial hybrid dynamic polymer crosslinked network. The supramolecular polymer dispersed therein having a degree of supramolecular cross-linking below its gel point may provide dynamic, in particular strain-responsive properties; whereas supramolecular polymer particles dispersed therein having a degree of supramolecular cross-linking above their gel point may provide packing and dynamic properties, allowing local viscosity and strength increase upon strain response.

According to a preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the crosslinking degree of the dynamic covalent bond crosslinking is below the gel point, the crosslinking degree of the hydrogen bond crosslinking is below the gel point, and the sum of the crosslinking degrees of the two is above the gel point. In this embodiment, the at least two types of dynamic covalent bonding crosslinks and hydrogen bonding crosslinks are in the same crosslinked polymer network structure, and since both the degree of crosslinking of the dynamic covalent bonding crosslinks and the degree of crosslinking of the hydrogen bonding crosslinks are below their gel points and the sum of them is above their gel points, dissociation of either of the dynamic covalent bonding and hydrogen bonding will result in destruction of the crosslinked structure, and the crosslinked structure change and properties of the polymer can be controlled by controlling conditions.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the degree of crosslinking by dynamic covalent bond crosslinking is below the gel point and the degree of crosslinking by hydrogen bond crosslinking is above the gel point. In the embodiment, the crosslinking degree of the hydrogen bond crosslinking is more than the gel point, so that the polymer material is favorably endowed with good self-repairing property and reusability under milder conditions, and the strength and viscoelasticity of the material matrix can be supplemented; the degree of crosslinking of the dynamic covalent bond crosslinks is below the gel point and can supplement hydrogen bonding.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the degree of crosslinking by dynamic covalent bond crosslinking is above the gel point and the degree of crosslinking by hydrogen bond crosslinking is below the gel point. In this embodiment, since the degree of crosslinking of the dynamic covalent bond crosslinks is above its gel point, it is capable of providing a viscoelastic and equilibrium structure to the substrate under certain conditions, and is also capable of exhibiting dynamic reversibility under other certain conditions; and the crosslinking degree of the hydrogen bond crosslinking is below the gel point, so that the material can be used as a supplement of a dynamic covalent bond to carry out rapid self-repairing and dynamic response on the material.

According to another preferred embodiment of the above invention, the composite hybrid dynamic polymer contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point. In this embodiment, since the degree of crosslinking of the dynamic covalent bond crosslinks is above its gel point, it is capable of providing a viscoelastic and equilibrium structure to the substrate under certain conditions, and is also capable of exhibiting dynamic reversibility under other certain conditions; the crosslinking degree of the hydrogen bond crosslinking is more than the gel point, so that the polymer material is endowed with good self-repairing property and reusability under a milder condition, and the strength and viscoelasticity of the material matrix can be supplemented.

In the preferred embodiment, the supramolecular polymer having a supramolecular crosslinking degree below the gel point and/or supramolecular polymer particles having a supramolecular crosslinking degree above the gel point may be dispersed in the hybrid dynamic polymer crosslinked network. The supramolecular polymer dispersed therein having a degree of supramolecular cross-linking below its gel point may provide dynamic, in particular strain-responsive properties; whereas supramolecular polymer particles dispersed therein having a degree of supramolecular cross-linking above their gel point may provide packing and dynamic properties, allowing local viscosity and strength increase upon strain response.

In addition, the present invention can also have other various dynamic polymer structure embodiments, one embodiment can comprise a plurality of same or different non-crosslinked polymer chains and/or crosslinked polymer networks, and the same crosslinked network can comprise different dynamic covalent crosslinks and/or different hydrogen bond crosslinks, wherein the hydrogen bond can interact with the dynamic covalent bond in the same crosslinked network or in each independent crosslinked network or part of the dynamic covalent crosslinked network, and can also be dispersed in the dynamic covalent crosslinked network in the form of a non-crosslinked polymer. The crosslinking degree of any crosslinking of any network in the combined hybrid dynamic polymer can be reasonably controlled so as to achieve the aim of regulating and controlling the balance structure and the dynamic performance; the crosslinking degrees of the dynamic covalent crosslinking and the hydrogen bonding crosslinking may be at least the respective gel point, at most the respective gel point, and preferably at least the respective gel point; when the dynamic covalent crosslinking reaches above the gel point, the dynamic polymer can maintain an equilibrium structure by virtue of the dynamic covalent crosslinking under specific conditions and can only exhibit dynamic characteristics by hydrogen bonds, and can exhibit complete dynamic reversibility under other specific conditions. In the present invention, when at least one crosslinking component is present, the different components (including the crosslinking component and the non-crosslinking component) may be dispersed, interspersed or partially interspersed with each other, but the present invention is not limited thereto. The structure of the combinatorial hybrid dynamic polymers of the present invention includes, but is not limited to, those mentioned above, and those skilled in the art can reasonably realize the structure according to the logic and context of the present invention.

In the present invention, the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure; once the dynamic covalent and hydrogen bonds are dissociated, the polymer system can be decomposed into any one or any several of the following secondary units: non-crosslinked units such as monomers, polymer chain fragments, polymer clusters, and the like, and even units such as crosslinked polymer fragments and the like; meanwhile, the dynamic polymer and the units can realize mutual transformation and dynamic reversibility through the bonding and the dissociation of dynamic covalent bonds and hydrogen bonds.

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

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

The term "ordinary covalent bond" as used herein refers to a covalent bond in the conventional sense other than dynamic covalent bond, which is difficult to break at ordinary temperature (generally not higher than 100 ℃) and ordinary time (generally less than 1 day), 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.

In embodiments of the present invention, the composite hybrid dynamic polymer and its composition and polymer chain topology in the feedstock components may be selected from the group consisting of non-crosslinked linear, cyclic, branched, clustered structures, and crosslinked structures and combinations thereof.

Wherein, the linear structure means that the polymer molecular chain is in a regular or irregular long-chain linear shape and is generally formed by connecting a plurality of repeating units on a continuous length, and the side group in the polymer molecular chain generally does not exist in a branched chain; 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.

Wherein, the "cyclic" structure refers to that the polymer molecular chain exists in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple rings, bridged ring, nested 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.

Wherein, 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 a linear chain end connected to a cyclic structure, a cyclic structure combined with a comb, a dendritic chain end connected to a cyclic chain, 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.

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

Wherein, the "cross-linked" structure refers to a three-dimensional infinite network structure of the polymer.

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

In the embodiment of the invention, the combined hybrid dynamic polymer and the composition and raw material components thereof can have only one topological form of polymer, and can also be a mixture of polymers with multiple topological forms.

In embodiments of the invention, the combination hybrid dynamic polymer may or may not have one or more glass transition temperatures. At least one of them is lower than 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or higher than 100 ℃ for the glass transition temperature of the composite hybrid dynamic polymer; wherein, the dynamic polymer with the glass transition temperature lower than 0 ℃ has better low-temperature service performance and is convenient to be used as sealing paste, sealing gum, elastomer, gel and the like; the dynamic polymer with the glass transition temperature of 0-25 ℃ can be used at normal temperature and can be conveniently used as an elastomer, sealing paste, sealing gum, gel, foam and common solid; the dynamic polymer with the glass transition temperature of 25-100 ℃ has stronger mechanical property, and is convenient to obtain common solid, foam and gel at room temperature; the dynamic polymer with the glass transition temperature higher than 100 ℃ has good dimensional stability, mechanical strength and temperature resistance, and is favorable for being used as a stress bearing material. The dynamic polymer with the glass transition temperature lower than 25 ℃ can show excellent dynamic property, self-repairing property and recyclability; for the dynamic polymer with the glass transition temperature higher than 25 ℃, the polymer can show good shape memory capacity and stress bearing capacity; in addition, due to the existence of the supermolecule hydrogen bond, the glass transition temperature of the dynamic polymer can be further regulated, and the dynamic property, the crosslinking degree and the mechanical strength of the dynamic polymer are supplemented. For the dynamic polymers of the present invention, it is preferred that at least one glass transition temperature is not greater than 50 deg.C, more preferably at least one glass transition temperature is not greater than 25 deg.C, and most preferably no glass transition temperature is greater than 25 deg.C. Systems that do not have a glass transition temperature above 25 c are particularly suitable for use as self-healing materials due to their good flexibility and flowability/creep at the temperatures of daily use. The glass transition temperature of the dynamic polymer can be measured by a glass transition temperature measurement method commonly used in the art, such as DSC and DMA.

In embodiments of the present invention, each raw material component of the combined hybrid dynamic polymer may have one or more glass transition temperatures, or may have no glass transition temperature, and at least one of the glass transition temperatures is lower than 0 ℃, or between 0 ℃ and 25 ℃, or between 25 ℃ and 100 ℃, or higher than 100 ℃, wherein the raw material of the compound with the glass transition temperature lower than 0 ℃ is convenient for low-temperature preparation and processing during the preparation of the dynamic polymer; the compound raw material with the glass transition temperature of 0-25 ℃ can be prepared, processed and molded at normal temperature; the compound raw material with the glass transition temperature of 25-100 ℃ can be molded by conventional heating equipment, and the manufacturing cost is low; the compound raw material with the glass transition temperature higher than 100 ℃ can be used for preparing high-temperature resistant materials with good dimensional stability and excellent mechanical properties. The dynamic polymer is prepared by utilizing a plurality of compound raw materials with different glass transition temperatures, so that the dynamic polymer with different glass transition temperatures in different ranges can be obtained, multiple comprehensive properties can be embodied, and the dynamic polymer has dynamic property and stability.

In embodiments of the invention, the polymer chain structure and its glass transition temperature may be altered chemically.

The combined hybrid dynamic polymer can contain the dynamic covalent bond at any suitable position of the polymer; the dynamic covalent bonds and the hydrogen bonds in the dynamic polymer may function both independently and synergistically. For non-crosslinked dynamic polymers, the polymer backbone may contain dynamic covalent bonds, or the polymer side chains/branches/branched chains backbone may contain dynamic covalent bonds; for the crosslinked dynamic polymer, the crosslinked network chain skeleton can contain dynamic covalent bonds, and the side chain/branched chain skeleton of the crosslinked network chain skeleton can also contain dynamic covalent bonds; the invention also does not exclude the inclusion of dynamic covalent bonds in the side and/or end groups of the polymer chain, other constituents of the polymer such as small molecules, fillers, etc. In embodiments of the present invention, the dynamic covalent bonds are preferably located on the backbone of the polymer backbone (for non-crosslinked structures) and on the backbone of the polymer crosslinked network chains (for crosslinked structures). The optional hydrogen bond, which may be constituted by hydrogen bond formation between hydrogen bond groups present at any one or more of the combined hybrid dynamic polymer structures; wherein, the hydrogen bond group can be present on a dynamic polymer cross-linked network chain skeleton, can also be present on a side chain/branched chain skeleton of the cross-linked network chain skeleton, and can also be present on a side group and an end group of the cross-linked polymer; or can be present on the main chain skeleton, side chain/branched chain skeleton, side group and end group of the non-crosslinked polymer; may also be present in the combined hybrid dynamic polymer composition, such as a small molecule compound or filler. The dynamic covalent bond and the hydrogen bond can be subjected to reversible fragmentation and regeneration under specific conditions; under appropriate conditions, dynamic covalent and hydrogen bonds at any position in the dynamic polymer can participate in dynamic reversible exchange.

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

The term "orthogonality" as used herein refers to different types of dynamic covalent bonds and different types of hydrogen bonds, which can exhibit different dynamic reactivity and dynamic reversibility under different external conditions due to different dynamic properties, stability, dynamic reaction conditions, etc., so that the dynamic polymer can exhibit dynamic reversible effects of different dynamic covalent bonds and hydrogen bonds under different environmental conditions. Specifically, dynamic covalent bonds do not generally exhibit dynamic reversibility at room temperature, and dynamic adjustment in a dynamic polymer system can be performed only through hydrogen bonds; after the system is heated, illuminated, added with an oxidation-reduction agent, added with a catalyst, added with an initiator, illuminated, radiated, microwave and plasma, and the pH is adjusted, the dynamic property of the dynamic covalent bond under corresponding conditions can be triggered, and different types of dynamic covalent bonds have different dynamic response capabilities to different environmental stimuli, for example, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, amine alkene-Michael addition dynamic covalent bonds are sensitive to the change of the pH value, dynamic siloxane bonds, unsaturated carbon-carbon double bonds capable of generating alkene cross metathesis reaction, unsaturated carbon-carbon triple bonds capable of generating alkyne cross metathesis reaction generally need to perform dynamic equilibrium reaction under the condition of the catalyst, and by utilizing the difference of reaction conditions, when one function is played, other functions are not triggered, and therefore orthogonality regulation is achieved.

The term "synergy" as used herein means that different types of dynamic covalent bonds and different types of hydrogen bonds are capable of exhibiting dynamic reactivity and dynamic reversibility having a synergistic effect under certain specific external conditions, so that the dynamic polymer exhibits a dynamic reversible effect more excellent than the original single effect under specific environmental conditions. By selecting dynamic covalent bonds or hydrogen bonds that are capable of dynamic behavior under the same external stimulus conditions of heating, adding redox agents, adding catalysts, light, radiation, microwaves, plasma effects, pH, etc., when one effect is effective, the other one or more effects can also exhibit dynamic behavior under corresponding environmental conditions, producing a synergistic effect greater than the linear superposition of the two effects. For example, dynamic sulfide linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effect, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, dynamic covalent linkage based on triazolinedione-indole, aminoalkene-michael addition dynamic covalent linkage, dynamic covalent linkage based on diazacarbene, dynamic exchangeable trialkylsulfonium linkage may exhibit different dynamics with respect to changes in temperature, and may exert synergistic effects under heating; acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds and amine alkene-Michael addition dynamic covalent bonds are sensitive to the change of pH value and can synergistically play a role through the adjustment of acidity and alkalinity; the dynamic siloxane bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross metathesis, and unsaturated carbon-carbon triple bonds that can undergo alkyne cross metathesis generally act synergistically by introducing a catalyst; by selecting proper reaction conditions and proper dynamic action, the cooperative regulation and control of the dynamic polymer can be realized.

In the invention, the dynamic sulfur-connecting bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, which can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic sulfur linkage described in the present invention is selected from, but not limited to, the following structures:

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

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

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

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

In the invention, the dynamic double selenium bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond are generated, thus showing the dynamic reversible characteristic; the dynamic diselenide bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating the dynamic bis-seleno bond includes but is not limited to temperature adjustment, addition of redox agent, addition of catalyst, addition of initiator, irradiation, radiation, microwave, plasma action and the like, so that the dynamic polymer shows good self-repairing property, recycling property, stimulation responsiveness and the like, for example, heating can lead the dynamic bis-seleno bond to be broken to form selenium free radical, so that dissociation and exchange reaction of the bis-seleno bond can be generated, the dynamic bis-seleno bond is reformed and stabilized after cooling, self-repairing property and reprocessing property can be displayed, the polymer containing the bis-seleno bond can obtain good self-repairing property by laser irradiation, free radical can be generated in the system by irradiation, microwave and plasma, and the dynamic repairing bis-seleno bond can be generated in the system to act with the dynamic repairing bis-seleno bond so that self-repairing property and reprocessing property can be obtained, the dynamic polymer can also be recycled by adding the redox agent in the system, wherein the dynamic bis-seleno bond can be promoted to be dissociated into alcohol, so that the polymer is dissociated, the dynamic initiator can be formed into bis-seleno-peroxide, the peroxide system can also include but is not limited to be generated, the peroxide-2-peroxide-2-ethyl-bis-benzoyl peroxide-ketone-2-disulfide (such as 2-ethyl-2-thiobenzone-2-bis-oxobenzene-2-bis-oxoacetone-bis-oxobenzene-oxoketone, bis-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoethyl-oxoketone, 2-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoketone, bis-oxoketone.

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

The dynamic selenium-nitrogen bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond are carried out, so that the dynamic reversible characteristic is embodied; the dynamic seleno-nitrogen bond described in the present invention is selected from, but not limited to, the following structures:

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

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

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

In an embodiment of the invention, the dynamic selenazonium bond contained in the dynamic polymer can be formed by reacting a phenyl seleno halide contained in the compound starting material with a pyridine derivative.

In the invention, the acetal dynamic covalent bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioketal bond, can be activated under certain conditions, and generates bond dissociation, ketal reaction and exchange reaction, thus showing dynamic reversible characteristics; the "certain conditions" for activating the dynamic reversibility of acetal dynamic covalent bond means heating, appropriate acidic aqueous conditions, and the like. The acetal-based dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

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

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

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

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

According to the invention, the dynamic covalent bond based on the carbon-nitrogen double bond comprises a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond and a dynamic acylhydrazone bond, and can be activated under certain conditions, and dissociation, condensation and exchange reactions of the dynamic covalent bond are carried out, so that the dynamic reversible characteristic is embodied; herein, the "certain condition" for activating the dynamic covalent bond dynamic reversibility based on a carbon-nitrogen double bond refers to an appropriate pH aqueous condition, an appropriate catalyst presence condition, a heating condition, a pressurizing condition, and the like. The dynamic covalent bond based on carbon-nitrogen double bond in the invention is selected from but not limited to at least one of the following structures:

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

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

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

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

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

In the invention, the dynamic covalent bond based on the reversible free radical can be activated under certain conditions to form a reversible oxygen/sulfur/carbon/nitrogen free radical, and generates bonding or exchange reaction of the bond, thus showing the dynamic reversible characteristic; the "exchange reaction of dynamic covalent bonds based on reversible free radicals" refers to that intermediate reversible free radicals formed after the dissociation of old dynamic covalent bonds in the polymer form new dynamic covalent bonds elsewhere, so that the exchange of chains and the change of the topological structure of the polymer are generated. The dynamic covalent bond based on reversible free radicals in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, X₁、X₂Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C_3-20Alkyl, divalent or polyvalent cyclic C_3-20Alkyl, phenyl, benzyl, aryl, carbonyl, sulfone, phosphate and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropylidene, isobutylene, isoamylidene, isohexylidene, cyclohexylidene, phenylene, benzylidene, carbonyl, sulfone, phosphate; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated, substituted, hybridized forms of the above groups and combinations thereof, R 'is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, methylbenzyl, R' is more preferably selected from the group consisting of methyl, ethyl, isopropyl, phenyl, benzyl; wherein each W is independently selected from an oxygen atom, a sulfur atom; w₁Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, preferably from ether groups; w₂Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof, preferably from the group consisting of thioether groups, secondary amine groups and substituents thereof, carbonyl groups; w₃Each independently selected from ether groups, thioether groups; w₄Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a divalent methyl group and substituents thereof, preferably from the group consisting of a direct bond, an ether group, a thioether group; w, W at different locations₁、W₂、W₃、W₄The structures of the two groups can be the same or different; wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R₁Preferably selected from hydrogen atom, hydroxy group, cyano group, carboxy group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaryl, substituted C_1-20Alkyl, substituted hetero C_1-20Alkyl radical, R₁More 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, and R at different positions₁May be the same or different; wherein R is₂Each independently selected from hydrogen atom, cyano group, hydroxy group, phenyl group, phenoxy group, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein L 'is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small hydrocarbon group, L' is preferably selected from the group consisting of acyl, acyloxy, acylthio, amido, oxyacyl, sulfuryl, phenylene, divalent C_1-20Alkyl, substituted divalent C_1-20Alkyl, substituted divalent C_1-20The heteroalkyl group, L 'is more preferably selected from acyl, oxyacyl, aminoacyl, phenylene, and L' at different positions may be the same or different; wherein V, V ' are independently selected from carbon atom and nitrogen atom, V, V ' at different positions can be the same or different, and when V, V ' is selected from nitrogen atom, it is connected with V, V

Is absent; wherein,

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein, X₁And X₂On

Can be connected into a ring, and can form the following structure:

wherein, the ring is nitrogen-containing aliphatic ring, nitrogen-containing aromatic ring or their combination with any number of elements, at least one ring atom is nitrogen atom, the hydrogen atom on the ring atom can be substituted by any substituent or not, the ring is preferably nitrogen-containing five-membered ring or nitrogen-containing six-membered ring, and is optimally selected from 2,2,6, 6-tetramethyl-piperidine, 4,5, 5-tetramethyl-imidazole, 2,5, 5-tetramethyl pyrrole, maleimide, succinimide and triazone. Typical dynamic covalent bond structures based on reversible free radicals may be mentioned, for example:

in an embodiment of the present invention, the "certain conditions" for activating dynamic reversibility of dynamic covalent bond based on reversible free radical include, but are not limited to, temperature adjustment, addition of initiator, light irradiation, radiation, microwave, plasma action, etc., for example, the dynamic covalent bond may be cleaved by heating to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed and stabilized after cooling, thereby allowing the polymer to obtain self-repairability and reworkability, the light irradiation may also cause the dynamic covalent bond to be cleaved to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed after removing light irradiation, microwave and the like, thereby obtaining self-repairability and reworkability, the initiator may generate free radical, thereby promoting dissociation or exchange of dynamic covalent bond, thereby obtaining self-repairability or recycling of repairability, wherein the initiator includes any one of the following initiators, such as photoinitiator, including, bis (2-tert-butyl) benzoyloxybenzoyl-2-bis (2-butyl-2-p-2-butyl-2-oxoethyl-2-bis (p-2-propyl-2-bis (4-butyl-oxoethyl-2-bis (p-propyl-2-propyl-p-2-propyl-2-bis (preferably-2-bis (di-tert-butyl-propyl-butyl-2-propyl-p-propyl-2-butyl-2-p-2-propyl-p-2-propyl-peroxybenzoylperoxy-2-butyl-2-propyl-2-peroxy-2-propyl-peroxy.

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

In the present invention, the binding exchangeable acyl bond can be activated under certain conditions and undergoes a binding acyl exchange reaction (e.g., a binding transesterification reaction, a binding amide exchange reaction, a binding carbamate exchange reaction, a binding vinylogous amide or vinylogous carbamate exchange reaction, etc.) with a nucleophilic group, thereby exhibiting a dynamic reversible property; wherein, the 'associative acyl exchange reaction' means that the associative exchangeable acyl bonds are firstly combined with nucleophilic groups to form an intermediate structure, and then the acyl exchange reaction is carried out to form a new dynamic covalent bond, thereby generating exchange of chains and change of a topological structure of the polymer, wherein the crosslinking degree of the polymer can be kept unchanged; wherein the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond means suitable catalyst existence conditions, heating conditions, pressurizing conditions, etc.; the "nucleophilic group" refers to a reactive group such as hydroxyl, sulfhydryl and amino group, which is present in a polymer system for a binding acyl exchange reaction, and the nucleophilic group may be on the same polymer network/chain as the binding exchangeable acyl bond, may be on a different polymer network/chain, or may be introduced through a small molecule or a polymer containing the nucleophilic group. The binding exchangeable acyl bond as described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

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

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

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

Among them, the catalyst for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) Montmorillonite KSF, hafnium tetrachloride (HfCl)₄)、Hf₄Cl₅O₂₄H₂₄、 HfCl₄KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as copper acetate; examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, copper acetate is preferable; sc (OTf)₃And HfCl₄Mixing and sharing synergistic catalysis; HfCl₄KSF-polyDMAP; the glycerol, the boric acid and the ferric nitrate hydrate are mixed to share the synergistic catalysis.

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

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

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

In the invention, the dynamic covalent bond based on steric effect induction contains a large group with steric effect, can be activated at room temperature or under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic. The steric effect induced dynamic covalent bond is selected from, but not limited to, at least one of the following structures:

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

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

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

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

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

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

In the invention, the reversible addition fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator, and a reversible addition fragmentation chain transfer reaction is carried out, so that the dynamic reversible characteristic is embodied. The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

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

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

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

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

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

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

In the invention, the dynamic siloxane bond can be activated under the condition of catalyst or heating, and siloxane exchange reaction is carried out, so that the dynamic reversible property is embodied; the term "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere with concomitant dissociation of old siloxane bonds, resulting in exchange of chains and a change in polymer topology. The dynamic siloxane bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

may be looped or not looped.

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

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

In the invention, the dynamic silicon ether bond can be activated under heating condition, and silicon ether bond exchange reaction is carried out, thus showing dynamic reversible characteristic; the "exchange reaction of the silyl ether bond" refers to the formation of a new silyl ether bond elsewhere with concomitant dissociation of the old silyl ether bond, resulting in exchange of the chains and a change in the topology of the polymer. The dynamic silicon ether linkage described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

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

In the invention, the exchangeable dynamic covalent bond based on the alkyl triazolium can be activated under certain conditions and has dynamic exchange reaction with the halogenated alkyl, thus showing dynamic reversible characteristics. The alkyl triazolium-based exchangeable dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

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

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

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

In the present embodiment, the "certain conditions" for activating the dynamic reversibility of exchangeable dynamic covalent bonds based on alkyltriazolium means in the presence of a halogenated alkyl group and a solvent and under suitable conditions of temperature, humidity and the like.

In the embodiment of the present invention, the raw material compound containing the alkyl triazolium-based exchangeable dynamic covalent bond is not particularly limited, but preferably contains an alkyl triazolium-based exchangeable dynamic covalent bond, an epoxy-based compound, an alkyl vinyl chloride, a vinyl chloride.

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

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

wherein Py is₃Is composed of

Mes is

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

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

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

wherein Py is₃Is composed of

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

In the embodiment of the present invention, the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction and the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction contained in the dynamic polymer may be derived from a selected polymer precursor already containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or may be generated or introduced on the basis of a polymer precursor not containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond. However, since the reaction conditions for forming the carbon-carbon double bond/carbon-carbon triple bond are generally harsh, it is preferable to use a polymer precursor having carbon-carbon double bond/carbon-carbon triple bond to carry out the reaction, thereby achieving the purpose of introducing carbon-carbon double bond/carbon-carbon triple bond.

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

In the invention, the [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein, the [2+2] cycloaddition reaction refers to a reaction that one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively provide 2 pi electrons to react and add with each other to form a quaternary ring structure. The [2+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

Can be linked to form a ring, on different atoms

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

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

In the embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [2+2] cycloaddition reaction between unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, cumulative diene groups, ketene groups contained in compound raw materials, or between the unsaturated carbon-carbon triple bonds and the compound raw materials, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in compound raw materials containing [2+2] cycloaddition dynamic covalent bonds, wherein the compound raw materials containing unsaturated carbon-carbon double bonds are preferably ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compounds, cyclooctene, norbornene, maleic anhydride, p-propargyl dicarboxylic acid, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene, and derivatives of the above compounds, and the like, and wherein the raw materials containing [2+2] cycloaddition dynamic covalent bond, the compound containing [2+2] cycloaddition, alkyne, isocyanate, the compound containing no limitation is particularly preferred.

In the invention, the [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group and 2 pi electrons are provided by a dienophile group to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

Can be linked to form a ring, on different atoms

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

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

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

wherein,

Can be linked to form a ring, on different atoms

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

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

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

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

Can be linked to form a ring, on different atoms

Can also be linked to form a ring, where K is preferred₁And K₂K to₃And K₄K to₅And K₆C to₁And C₂C to₃And C₄C to₅And C₆Forming a ring; the 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:

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

C₅and C₆The ring formed between preferably has the following structure:

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

In the embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [4+2] cycloaddition reaction between a compound raw material containing a diene group and a compound raw material containing a dienophile group, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a [4+2] cycloaddition dynamic covalent bond, wherein the compound raw material containing a diene group may be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives thereof, and wherein the compound raw material containing a dienophile group may be selected from ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compound, cyclooctene, norbornene, maleic acid, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisanhydride, maleimide, and compounds containing a cyclic addition of more preferably a compound containing a 4+ 2-epoxy group, a maleimide group, a compound containing a cycloaddition of a maleimide group, a more preferably a compound containing a fullerene group, a compound, a sulphur, a compound containing a mercapto group, and a compound containing a more preferably a cycloaddition of a 4+ 2-epoxy group, a compound.

In the invention, the [4+4] cycloaddition dynamic covalent bond is formed based on the [4+4] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing dynamic reversible characteristics; wherein the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 pi electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

Can be linked to form a ring, on different atoms

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

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

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

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

in the invention, the dynamic covalent bond of the mercapto-Michael addition can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing the dynamic reversible characteristic; the dynamic covalent thiol-michael addition bond described in the present invention is selected from, but not limited to, at least one of the following structures:

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

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

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

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

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

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

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

In the invention, the amine alkene-Michael addition dynamic covalent bond can be activated under a certain condition, and the dissociation, bonding and exchange reaction of bonds occur, thus showing the dynamic reversible characteristic; the amine alkene-michael addition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

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

In the invention, the dynamic covalent bond based on triazolinedione-indole can be activated under certain conditions, and the bond dissociation, bonding and exchange reaction occur, so that the dynamic reversible characteristic is embodied; the dynamic covalent bond based on triazolinedione-indole described in the present invention is selected from, but not limited to, the following structures:

wherein,

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

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

In the invention, the dynamic covalent bond based on the dinitrogen heterocarbene can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond are generated, thus showing the dynamic reversible characteristic; the dinitrogabine-based dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein,

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

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

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

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

In an embodiment of the present invention, the dynamic covalent bond based on the diazacarbone contained in the dynamic polymer may be formed by using the diazacarbone group contained in the compound raw material itself or by reacting it with a thiocyano group.

In the invention, the hexahydrotriazine dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction are carried out, thus showing dynamic reversible characteristics; the "certain condition" for activating the dynamic reversibility of the hexahydrotriazine dynamic covalent bond refers to an appropriate pH condition, heating condition, or the like. The hexahydrotriazine dynamic covalent bond in the invention is selected from but not limited to at least one of the following structures:

wherein,

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

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

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

In the invention, the dynamic exchangeable trialkyl sulfonium bond can be activated under the heating condition and undergoes alkyl exchange reaction, thus showing dynamic reversible characteristics; wherein the "transalkylation reaction" refers to the formation of new trialkylsulfonium bonds elsewhere with concomitant dissociation of old trialkylsulfonium bonds, resulting in exchange of chains and changes in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under the heating conditions of 130-160 ℃. The dynamically exchangeable trialkylsulfonium linkage described in this invention is selected from, but not limited to, the following structures:

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

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

The dynamic covalent bond in the invention can be kept stable under specific conditions, thus achieving the purpose of providing a balanced structure and mechanical strength, and can also show dynamic reversibility under other specific conditions, so that the material can be completely self-repaired, recycled and plastically deformed; meanwhile, due to the existence of different types of dynamic covalent bonds, the polymer can show different response effects to external stimuli such as heat, illumination, pH, oxidation reduction and the like, and dynamic reversible balance can be promoted or slowed down in a proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.

combination 1: dynamic linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, triazolinedione-indole-based dynamic covalent linkage, aminoalkene-michael addition dynamic covalent linkage, dinitrohetero carbene-based dynamic covalent linkage, dynamic exchangeable trialkylsulfonium linkage combinations. The dynamic reversible balance of the dynamic covalent bonds can be realized by means of temperature regulation, illumination, initiator addition and the like, the operation is simple and convenient, the cost is low, and the dynamic reaction balance process can be controlled by regulating and controlling the temperature and the illumination frequency;

and (3) combination 2: at least two of dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, and amine alkene-Michael addition dynamic covalent bond combinations. The dynamic covalent bond selected in the combination is sensitive to the change of pH value, has faster dynamic reaction capability, is generally suitable for preparing gel materials, and can realize the control of dynamic equilibrium reaction and the gel-sol transformation of polymer materials by regulating and controlling the pH value of a swelling agent;

and (3) combination: at least two of dynamic siloxane bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross-metathesis reactions, unsaturated carbon-carbon triple bonds that can undergo alkyne cross-metathesis reactions, [2+2] cycloaddition dynamic covalent bonds, [2+4] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-michael addition dynamic covalent bonds, and combinations of dynamic covalent bonds based on triazolinedione-indole. The dynamic covalent bond selected in the combination generally needs to perform dynamic equilibrium reaction of the dynamic covalent bond in the presence of a catalyst, and after the catalyst or a composite component containing the catalyst is added into a system, the dynamic covalent bond can show dynamic characteristics under mild conditions.

In the embodiment of the present invention, in the process of introducing a dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in a raw material of a compound having a dynamic covalent bond, the type and mode of reaction for introducing a dynamic covalent bond are not particularly limited, and the following reaction is preferred: the reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl and epoxy group, the reaction of carboxylic acid, acyl halide, acid anhydride and active ester with amino, hydroxyl and mercapto, the reaction of epoxy group with amino, hydroxyl and mercapto, thiol-ene click reaction, acrylate free radical reaction, acrylamide free radical reaction, double bond free radical reaction, Michael addition reaction of alkene-amine, azide-alkyne click reaction, tetrazole-alkene cycloaddition reaction and silicon hydroxyl condensation reaction; more preferably, the reaction can be carried out rapidly at a temperature of not higher than 100 ℃, including but not limited to the reaction of isocyanate group with amino group, hydroxyl group, mercapto group, carboxyl group, the reaction of acyl halide, acid anhydride with amino group, hydroxyl group, mercapto group, acrylate radical reaction, acrylamide radical reaction, and thiol-ene click reaction.

The reactive group in the embodiments of the present invention refers to a group capable of undergoing chemical reaction and/or physical action to form a common covalent bond and/or dynamic covalent bond and/or hydrogen bond spontaneously or under the conditions of an initiator or light, heating, irradiation, catalysis, etc., and suitable groups include, but are not limited to: hydroxyl, carboxyl, carbonyl, acyl, amide, acyloxy, amino, aldehyde, sulfonic, sulfonyl, thiol, alkenyl, alkynyl, cyano, oxazinyl, oxime, hydrazine, guanidino, halogen, isocyanate, anhydride, epoxy, hydrosilyl, acrylate, acrylamide, maleimide, succinimide, norbornene, azo, azide, heterocyclic, triazolinedione, carbon, oxygen, sulfur, selenium, hydrogen bonding, and the like; hydroxyl, amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, acrylamide, oxygen radical, sulfur radical, hydrogen bonding group are preferred. The reactive group plays a role in a system, namely, derivatization reaction is carried out to prepare a hydrogen bond group, and common covalent bond and/or dynamic covalent bond and/or hydrogen bond are directly formed between the compound per se or between the compound and other compounds or between the compound and reaction products of the compound through the reaction of the reactive group, so that the molecular weight of the compound and/or the reaction products of the compound is increased/the functionality of the compound is increased, and polymerization or crosslinking is formed between the compound and/or the reaction products of the compound.

The hydrogen bond in the present invention is any suitable supramolecular interaction established by hydrogen bond, and is generally a hydrogen bond link between Z and Y through hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, which is mediated by hydrogen, to form 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, and is selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably from F, N, O atom, and more preferably from O, N atom. 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, preferably at least part of hydrogen bond groups play a role of supramolecular crosslinking.

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.

The more the number of teeth of 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 dynamic 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, the dynamic nature of the hydrogen bonding is strong, and dynamic properties can be provided together with dynamic covalent bonds. 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 generated by non-covalent interactions that exist between any suitable hydrogen bonding groups. The hydrogen bond group may contain only a hydrogen bond donor, only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.

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

more preferably contains

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

wherein A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atom and mono-substituted alkyl; x is selected from halogen atoms.

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

the side hydrogen bond group in the invention comprises a side group hydrogen bond group, a side chain skeleton hydrogen bond group and a side chain end group hydrogen bond group. Wherein, the pendant hydrogen bond group refers to a hydrogen bond group existing on a pendant group of a polymer chain skeleton (including a main chain and a side chain/branched chain skeleton), and the pendant hydrogen bond group can also exist on a multistage structure of the pendant group; the side chain skeleton hydrogen bond group refers to a hydrogen bond group existing on the skeleton of a side chain (including a branched chain and a forked chain) of a polymer chain, and the side chain skeleton hydrogen bond group can also exist on the multilevel structure of the side chain; side chain end hydrogen bonding groups refer to hydrogen bonding groups present on the end groups of side chains (including branched and forked chains) of polymeric chains, and side chain end hydrogen bonding groups may also be present on the multilevel structure of the side chains.

In the embodiment of the present invention, the side hydrogen bonding group preferably contains any one or more of the following structural components:

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

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; i, D, Q wherein any two or more of them may be linked together to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof; 3. the cyclic group structure in 6 is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, and at least two ring-forming atoms are nitrogen atoms, the cyclic group structure is preferably selected from 3-50 membered rings, more preferably from 3-10 membered rings; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on the respective ring-forming atoms may or may not be substituted. In embodiments of the present invention, the pendant hydrogen bonding groups are preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, pyrazoles, imidazoles, imidazolines, triazoles, purines, porphyrins, and derivatives of the above groups.

Examples of suitable pendant hydrogen bonding groups, pendant end hydrogen bonding groups are, but the invention is not limited to:

suitable side chain backbone (including branched and forked chains) hydrogen bonding groups are exemplified by (but the invention is not limited to):

wherein m and n are the number of repeating units, and may be fixed values or average values, and are preferably less than 20, and more preferably less than 5.

Pendant hydrogen bonding groups have structural diversity including, but not limited to, hydrogen bonding donor and acceptor numbers, group size, length and rigidity of the linkage to the polymer chain; in addition, the number of pendant hydrogen bonding groups attached to the polymer chain is also widely adjustable. The side hydrogen bond groups participate in forming hydrogen bonds, so that the hydrogen bond effect with the strength, the dynamic property, the responsiveness and the crosslinking density adjustable in a large range can be obtained, meanwhile, the dynamic property of the hydrogen bonds, the glass transition temperature of the crosslinked polymer and the like can be controlled through regulating and controlling the linkage with the polymer chain, various dynamic properties of the hybrid dynamic polymer can be effectively regulated and controlled, and the polymer material with richer structure, more diversified performance and more hierarchical dynamic reversible effect is obtained. Meanwhile, as the side hydrogen bond group is positioned on the polymer side group and/or the side chain, the movement of the group and the chain is more free, the dynamic property is stronger, and the self-repairing and the dynamic property adjustment are particularly facilitated.

In the embodiment of the invention, the combined hybrid dynamic polymer optionally contains suitable hydrogen bonding actions formed by participation of main chain skeleton hydrogen bonding groups and/or main chain end group hydrogen bonding groups, including intermolecular crosslinking, intramolecular cyclization, intermolecular polymerization and the like, so as to enrich the performance and adjustability of the dynamic polymer.

The backbone skeleton hydrogen bonding group referred to in the present invention refers to a hydrogen bonding group present on a backbone of a polymer backbone (including a non-crosslinked polymer backbone and a dynamically crosslinked polymer network chain backbone) in which at least a part of atoms are constituents of the backbone skeleton, and preferably contains the following structural components:

in the embodiment of the present invention, the main chain skeleton hydrogen bonding group and the main chain terminal hydrogen bonding group are preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazoles, imidazoles, imidazolines, triazoles, purines, porphyrins, derivatives thereof, and the like.

Suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):

the main chain end group hydrogen bond group in the invention refers to a hydrogen bond group existing on the end group of the main chain of the polymer, and the preferable structure can refer to the side group hydrogen bond group and the side chain end group hydrogen bond group, which is not described herein again.

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

the hydrogen bond groups on other optional components in the composition of the combined hybrid dynamic polymer, such as small molecules, polymers and fillers, can refer to the side hydrogen bond groups, the main chain skeleton hydrogen bond and the main chain end group hydrogen bond groups, and are not described again here.

In the invention, the same hybrid dynamic polymer can contain one or more than one hydrogen bonding group, and the same cross-linking network can also contain one or more than one hydrogen bonding group, that is, the dynamic polymer can contain one hydrogen bonding group or the combination of a plurality of hydrogen bonding groups. The hydrogen bonding groups may be formed by any suitable chemical reaction, 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 ester group and amino, hydroxyl, sulfhydryl groups.

In embodiments of the invention, hydrogen bonding groups may be introduced in any suitable composition and at any suitable time, including but not limited to from monomers, while forming a prepolymer, while forming a dynamic covalent crosslink, after forming a dynamic covalent crosslink. Preferably at the same time as the prepolymer is formed and the covalent crosslinking is dynamic. In order to avoid the influence of the formation of hydrogen bond crosslinking after the introduction of the hydrogen bond group on the operations of mixing, dissolving and the like, the hydrogen bond group can also be subjected to closed protection, and then the deprotection is carried out after a proper time (such as the formation of dynamic covalent crosslinking at the same time or after).

The invention fully utilizes dynamic differences among various dynamic covalent bonds and hydrogen bonds, exerts orthogonality and cooperativity effects, and obtains the dynamic polymer with self-repairing, recoverable and reusable characteristics, and because the strength and the dynamic properties of different types of dynamic covalent bonds are different, the structures and the performances of different hydrogen bonds are also different, the strength, the dynamic property, the responsiveness and the like of the dynamic polymer can be adjusted in a large range on the basis of containing at least two types of dynamic covalent bonds and adding the hydrogen bonds; meanwhile, different dynamic covalent bonds are selected, so that the dynamic polymer can show different dynamic response effects on the stimulation conditions of heat, illumination, pH, oxidation reduction and the like; in addition, by regulating and controlling parameters such as molecular structure, functional group number, molecular weight and the like of a compound serving as a raw material, a dynamic polymer with different structures and apparent characteristics, adjustable performance and wide application can be prepared, and the dynamic polymer can be conveniently combined and hybridized by regulating and controlling the number of introduced dynamic covalent bonds and hydrogen bonds and the linking structure of the dynamic covalent bonds and the hydrogen bonds with a polymer chain, so that the dynamic polymer and the combined hybrid polymer with controllable glass transition temperature are obtained.

The topology of the linking group for linking the dynamic covalent bond and/or the hydrogen bond group is not particularly limited, and may be linear, branched, multiarm, star, H, comb, dendrimer, monocyclic, polycyclic, spiro, fused ring, bridged ring, chain with cyclic structure, two-dimensional and three-dimensional cluster types and combinations thereof, and the topology of the linking group is preferably linear, branched, star, comb, dendrimer, two-dimensional and three-dimensional cluster types, more preferably linear or branched. For the linking group with straight chain type and branched chain type structures, the molecular chain motion energy barrier is low, the molecular chain motion capability is strong, the processing and forming are facilitated, the polymer can show quick self-repairing performance and sensitive stress/strain response capability, and the dynamic polymer with quick self-repairing performance, recyclable and reusable characteristics and good processing performance can be obtained. For the connecting base with two-dimensional and three-dimensional cluster structures, the topological structure is stable, and good mechanical property, thermal stability, solvent resistance and creep resistance can be provided for the dynamic polymer.

For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or. For example, the term "and/or" in the specification, in which a dynamic covalent bond and a hydrogen bond are present as a polymerization linking point and/or a crosslinking linking point of a dynamic polymer means that the dynamic covalent bond and the hydrogen bond are present as a polymerization linking point of the dynamic polymer, or the dynamic covalent bond and the hydrogen bond are present as a crosslinking linking point of the dynamic polymer, or the dynamic covalent bond and the hydrogen bond are present as a polymerization linking point and a crosslinking linking point of the dynamic polymer. As another example, the term "comprising dynamic covalent and hydrogen bonds at the side groups and/or end groups of the polymer chains" refers to the term "comprising dynamic covalent and hydrogen bonds at the side groups of the polymer chains, or comprising dynamic covalent and hydrogen bonds at the end groups of the polymer chains, or comprising dynamic covalent and hydrogen bonds at the side groups and end groups of the polymer chains. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.

The combined hybrid dynamic polymer at least comprises two dynamic covalent bonds, and the strength, structure, dynamic property, responsiveness, formation conditions and the like of the dynamic covalent bonds of different types are different, so that a synergistic and orthogonal dynamic effect and response effect can be achieved, and the structure and performance of the material are more adjustable. In addition, by selectively controlling other conditions (such as adding auxiliary agents, adjusting reaction temperature, performing illumination and the like), the dynamic covalent chemical equilibrium can be accelerated or quenched to be in a required state under a proper environment.

The dynamic reversible property is usually obtained by means of temperature regulation, redox agent addition, catalyst addition, illumination, radiation, microwave, plasma action, pH regulation and the like, wherein the temperature regulation means which can be adopted in the invention comprises but is not limited to water bath heating, oil bath heating, electric heating, microwave heating, laser heating and the like, the type of illumination adopted in the invention is not limited, Ultraviolet (UV), infrared light, visible light, laser, chemiluminescence, more preferably ultraviolet light, infrared light and visible light are preferred, the radiation adopted in the invention comprises but is not limited to high-energy ionizing rays such as α rays, β rays, gamma rays, x rays, electron beams and the like, the plasma action adopted in the invention refers to catalysis by ionized gas-like substances consisting of positive and negative ions generated after atoms and atomic groups are ionized after part of electrons are deprived, and the microwave frequency adopted in the invention refers to electromagnetic waves of 300MHz to 300 GHz.

In the embodiment of the invention, the form of the combined hybrid dynamic polymer can be solution, emulsion, paste, gum, common solid, elastomer, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), 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%. Solutions, emulsions, pastes, glues, ordinary solids, elastomers, gels, and foams are characterized and advantageous. The solution and the emulsion have good fluidity, can fully show a shear thickening effect in fluid, and can prepare a self-repairing coating by utilizing the coating property of the solution and the emulsion. Pastes are typically concentrated emulsions and gums are typically concentrated solutions or low glass transition temperature polymers that can exhibit good plasticity and fillability. 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, which is beneficial for providing good resilience and toughness. The gel has good flexibility and can show better variability and rebound resilience. The foam material has the advantages of low density and lightness, can overcome the problems of brittleness of partial common solid and low mechanical strength of gel, and has good elasticity and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

In the embodiment of the invention, the combined hybrid dynamic polymer gel can 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 can be obtained by swelling with the swelling agent after the preparation of the dynamic polymer is finished. 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 dynamic polymer foam material, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted to foam the dynamic polymer.

The mechanical foaming method is that during the preparation of dynamic polymer, large amount of air or other gas is introduced into emulsion, suspension or solution of polymer via strong stirring to form homogeneous foam, which is then physically or chemically changed to form foam. 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 dynamic 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/foaming microsphere method is that hollow microspheres are added into the material and then compounded to form closed-cell foamed polymer; (5) a filling foamable particle method of mixing filled foamable particles first and then foaming the foamable particles in a molding or mixing process to obtain a foamed polymer material; (6) the freeze-drying method is that the dynamic polymer is swelled in a volatile solvent to be frozen, and then the solvent is escaped in a sublimation manner under the condition of approximate vacuum, thereby obtaining the porous sponge-like foam 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 chemical foaming method is a method for generating gas and foaming along with chemical reaction in the dynamic polymer foaming process, and includes, but is not limited to, the following methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) to cause the polymer to expand and foam. 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 an embodiment of the present invention, the structure of the dynamic polymer foam material relates to three structures, namely an open-cell structure, a closed-cell structure and a semi-open and semi-closed structure; dynamic polymer foams are classified according to their hardness into three categories, soft, hard and semi-hard; dynamic polymer foams can be further classified by their density into low-foaming, medium-foaming and high-foaming.

The initiator, catalyst and redox agent for activating/adjusting the dynamic covalent bond equilibrium reaction according to the present invention can be directly dispersed in the polymer component, or can be used in the form of a composite, for example, coated or loaded on an organic, inorganic or polymer carrier by a physical or chemical method, and coated in a microcapsule or a microcatheter together with other components having high fluidity under dynamic reaction conditions. When the initiator, catalyst and redox agent are used alone, they are compatible with the polymer components and optionally various groups of the various auxiliary fillers. The reasonable selection of the carrier can enhance the dispersibility of the initiator, the catalyst, the redox agent or the compound component thereof in the polymer component and reduce the particle size of the cluster, thereby improving the reaction efficiency, reducing the use amount and lowering the cost. Proper selection of the coating material also avoids deactivation of the additive during the preparation or operation of the composition.

The organic carrier for coating the initiator, the catalyst and the redox agent is not particularly limited, and examples of the organic carrier can be selected from paraffin, polyethylene glycol and the like, the method for coating the additive in the organic carrier is a known and disclosed technical means, and a common preparation method is selected for the invention. For example, a preferred preparation method for coating with paraffin as the organic carrier is: fully blending the selected additive, paraffin and surfactant in a paraffin melting state, and pouring the blend into water which is stirred at a certain rotating speed and has the temperature higher than the melting point of the paraffin; stirring until the blending liquid reaches a stable state, and adding ice water to quickly cool the water to below the melting point of paraffin; stopping stirring, and filtering to obtain the paraffin-coated composite component.

The carrier for loading the initiator, the catalyst and the redox agent on the organic or inorganic carrier through physical adsorption or chemical reaction is not particularly limited, and can be selected from polystyrene resin particles, magnetic nanoparticles, silica gel particles, molecular sieves, other mesoporous materials and the like as examples, a method for loading the additive on the organic or inorganic carrier is a known and disclosed technical means, and a common preparation method is selected in the invention.

The present invention also allows for the encapsulation of initiators, catalysts, redox agents and other optional adjuvants in polymer-shell microcapsules. Among them, the polymer as the outer wall of the microcapsule is not particularly limited, and includes, but is not limited to, the following: natural polymers such as gum arabic, agar, etc., semisynthetic polymers such as cellulose derivatives, and synthetic polymers such as polyolefin, polyester, polyether, polyurethane, polyurea-aldehyde, polyamide, polyvinyl alcohol, polysiloxane, etc., and the usual preparation method is selected for the present invention.

In the preparation process of the combined hybrid dynamic polymer, in addition to the initiator, the catalyst and the redox agent which are used for activating/adjusting the dynamic covalent bond dynamic equilibrium reaction, certain solvent, other auxiliary agents/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.

The other additive/additive which can be added/used can improve the material preparation process, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance. The auxiliary agent is selected from any one or any several of the following auxiliary agents: auxiliary agents for synthesis, including catalysts; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; an auxiliary agent for improving mechanical properties, comprising a toughening agent; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer and a foaming agent; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents include nucleating agents, rheological agents, thickening agents and leveling agents.

The fillers that can be added/used include, but are not limited to, inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, molybdenum disulfide, silica, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano silica, nano Fe₃O₄Particulate, nano gamma-Fe₂O₃Particulate, nano MgFe₂O₄Particulate, nano-MnFe₂O₄Granular, nano CoFe₂O₄Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)₄:Er、CaF₂:Er、Gd₂(MoO₄)₃:Er、Y₂O₃:Er、Gd₂O₂S:Er、 BaY₂F₈:Er、LiNbO₃:Er,Yb,Ln、Gd₂O₂:Er,Yb、Y₃Al₅O₁₂:Er,Yb、TiO₂:Er,Yb、YF₃:Er,Yb、Lu₂O₃:Yb,Tm、 NaYF₄:Er,Yb、LaCl₃:Pr、NaGdF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Ln, NaYF₄:Yb,Tm、Y2BaZnO₅:Yb,Ho、NaYF₄:Yb,Er@NaYF₄Core-shell nanostructures of Yb, Tm, NaYF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the heat generating function under the action of infrared and/or near-infrared light and/or electromagnetic is preferably selected from graphene, graphene oxide, carbon nanotube, nano-Fe₃O₄The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. Good heating performance, especially remote control heating performance, and is beneficial to obtaining controllable shape memory, self-repairing performance and the like. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.

The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-CoPt₃Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other particles with high magnetic property in infrared,Nano metal particles capable of generating heat under at least one action of near infrared, ultraviolet and electromagnetism, and the like; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.

The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.

Wherein, the type of the added filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred₃O₄Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the present invention, the filler may be selectively passedThe polymer chain is subjected to dispersion compounding or direct connection after modification, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the method has important significance for the actions of photo-thermal, electromagnetic heat and the like.

In the preparation process of the hybrid dynamic polymer, the addition amount of each component of the dynamic polymer is not particularly limited, and can be adjusted by those skilled in the art according to the actual preparation situation and the target polymer performance.

The combined hybrid dynamic polymer contains different kinds of dynamic covalent bonds and optional hydrogen bonds, and can show orthogonal dynamic responsiveness and various dynamic reversible effects, so that the unique performance is shown; through proper component selection and formula design, the obtained polymer material can be widely applied to the fields of military aerospace equipment, functional coatings, biomedicine, biomedical materials, self-repairing materials, buildings, energy sources, bionics and the like.

For example, by utilizing the dynamic reversibility of dynamic covalent bonds and hydrogen bonds, the adhesive with the self-repairing function can be prepared, and can be applied to the adhesion of various materials, such as the adhesive for the electrode of a battery/super capacitor and the separator, so as to reduce the damage of the electrode and prolong the service life of the electrode material; the preparation method can also be used for preparing polymer plugging glue with good plasticity, recoverability and reusability, and sealing elements such as sealing plugs, sealing rings and the like, and can be widely applied to the aspects of electronic appliances, pipeline sealing and the like; the method can also be applied to the preparation of self-repairing and tear-resistant instrument equipment or kits; based on the dynamic reversibility of dynamic covalent bonds and hydrogen bonds, the scratch-resistant coating with the self-repairing function can be designed and prepared, so that the service life of the coating is prolonged, and long-acting anticorrosion protection on a substrate material is realized; through proper component selection and formula design, the polymer gasket or the polymer plate with the self-repairing function can be prepared, so that the principle of organism injury healing can be simulated, the material can carry out self-healing on internal or external injuries, hidden dangers are eliminated, the service life of the material is prolonged, the bionic effect is embodied, the recoverable characteristic and the recycling capability of the material are realized, and the material has great application potential in the fields of military industry, aerospace, electronics, bionics and the like.

For another example, by combining the differences in stimulus responsiveness of different types of dynamic covalent bonds in the hybrid dynamic polymer, a polymer material having different stimulus-dependent and dynamic response effects can be prepared. For example, different dynamic covalent bonds can be selected, so that the dynamic polymer can show different response effects to stimulation conditions such as heat, illumination, pH, oxidation reduction and the like, and can be applied to the manufacture of intelligent materials such as a thermal response type shape memory material, a pH response type gel, a photochromic material, a drug controlled release system and the like, and the polymer material can show multiple response effects due to the existence of different dynamic covalent bonds.

For another example, various dynamic covalent bonds and hydrogen bonds are introduced, so that the polymer material can show excellent toughness under appropriate conditions, and a polymer film, a fiber or a plate with excellent toughness can be obtained; through dynamic equilibrium reaction in the polymer, internal defects of the material caused by internal stress can be effectively reduced, so that the obtained polymer material has better performance; the polymer material can also be applied to the preparation of coating materials with viscous flow property and high elasticity conversion, energy storage devices and the like, and the preparation of toys and body-building materials with viscous-elastic magic conversion effect.

In addition, the combined hybrid dynamic polymer can be applied to other various suitable fields according to the embodied performance, and the technical personnel in the field can expand and implement the combined hybrid dynamic polymer according to the actual needs.

The dynamic polymer materials of the present invention are further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.

Example 1

Preparing a diol monomer 1 by carrying out thiol-ene click reaction on divinyl glycol and N- [ (2-mercaptoethyl) carbamoyl ] propionamide, and synthesizing polyethylene oxide with a hydrogen bond group on a side group by using the diol monomer 1 and ethylene oxide as raw materials and boron trifluoride diethyl etherate as a catalyst through cationic ring-opening polymerization; then the diol compound (a) is prepared by respectively carrying out esterification reaction and thiol-ene click addition reaction on the diol compound (a), acrylic acid and 1-mercaptopropan-2-ol.

Adding a certain amount of tetrahydrofuran solvent into a three-neck flask, then adding 0.01mol of glycol compound (a), 0.02mol of aldehyde group single-ended polyethylene glycol and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, carrying out reflux reaction at 65 ℃ for 6h under the protection of nitrogen, cooling to room temperature to obtain a semitransparent viscous sample, and using the viscous sample as a viscosity regulator.

Example 2

Using AIBN as an initiator and triethylamine as a catalyst, and sequentially reacting 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine with quantitative N- [ (2-mercaptoethyl) carbamoyl ] propionamide and 3-mercapto-1, 2-propanediol by a mercaptan-olefin click addition reaction to prepare the polyol compound (a).

Weighing 0.01mol of polyol compound (a), dissolving in 200ml of tetrahydrofuran solvent, adding 0.04mol of aldehyde group single-ended polyethylene glycol and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, carrying out reflux reaction at 65 ℃ for 6h under the protection of nitrogen, adding 2 wt% of calcium carbonate and 2 wt% of titanium dioxide, continuing to react for 2h, pouring a polymer solution with a certain viscosity into a mold, placing the mold in a 60 ℃ oven for further reaction, cooling to room temperature, standing for 30min, and cooling to room temperature to obtain a white viscous sample, wherein the white viscous sample can be used as a tackifier with self-repairing property.

Example 3

Methyl vinyl silicone oil with molecular weight of about 3,000 and 3-mercapto-1-propanol are taken as raw materials, a proper amount of DMPA is added as a photoinitiator, and the modified silicone oil (a) is prepared by thiol-ene click reaction under the condition of ultraviolet irradiation. Using ethanethiol and isocyanate ethyl acrylate as raw materials, reacting to obtain acrylate containing thiocarbamate groups, and then using DMPA as a photoinitiator to react with methyl mercapto silicone oil with the molecular weight of about 30,000 to prepare hydrogen bond group graft modified silicone oil (b) through thiol-ene click reaction under the condition of ultraviolet irradiation.

20ml of modified silicone oil (a) and 0.12mol of siloxane compound (c) are sequentially added into a dry and clean three-neck flask and heated to 80 ℃ for reaction for 4h, then 0.12mol of dimercapto compound (d), hydrogen bond group grafted modified silicone oil (b) and 0.2 wt% of photoinitiator DMPA are added and uniformly mixed, the mixture is reacted for 30min under the irradiation of ultraviolet light, then the mixture is cooled to room temperature and placed for 30min, finally, polymer colloid with certain viscoelasticity is obtained, the surface of the polymer colloid has certain viscosity, excellent tensile toughness is achieved through the synergistic effect of dynamic covalent bonds and hydrogen bonds, a polymer sample is slightly heated after being pulled apart, the broken sample can be automatically bonded again, and the polymer can be used as a rubber adhesive with self-repairing property or a casting agent.

Example 4

Taking methyl mercapto silicone oil with molecular weight of about 30,000 and dimethyl dithio-amino-methyl-allyl-carbamate as raw materials, taking DMPA as a photoinitiator, and preparing the silicone oil (a) containing disulfide ester side groups by thiol-ene click reaction under the condition of ultraviolet irradiation. Methyl vinyl silicone oil with molecular weight of about 30,000 and N- [ (2-mercaptoethyl) carbamoyl ] propionamide are used as raw materials, DMPA is used as a photoinitiator, and the silicone oil (b) containing hydrogen bond groups is prepared by thiol-ene click reaction under the condition of ultraviolet irradiation. The diene double-end-capped silicone oil is prepared by using hexadienol and hydroxyl silicone oil with the molecular weight of about 500 as raw materials, controlling the molar ratio of the hexadienol and the hydroxyl silicone oil to be 2:1 and performing hydrolytic condensation.

Adding 200ml of THF (tetrahydrofuran), then adding 20g of silicone oil (a) containing disulfide ester side groups, 5.8g of diene double-end-capped silicone oil and 15g of silicone oil (b) containing hydrogen bond groups, taking a proper amount of zinc chloride as a catalyst, heating to 50 ℃, stirring and dissolving, then adding 1.2g of tetramethylammonium hydroxide and 0.8g of sodium glycerol, continuing to react for 2h, then continuing to stir and react for 24h at 50 ℃, then placing the sample in a vacuum oven at 50 ℃ to obtain a polymer colloid with certain viscoelasticity, wherein the surface of the polymer sample is soft and has super-toughness, the polymer sample can be stretched and expanded in a large range under the action of external stress, and after the polymer sample is broken, stress is slightly applied to the section, and the sample can be bonded by itself to achieve a good self-repairing effect. The obtained polymer colloid can be used as a recyclable electronic encapsulating material.

Example 5

Reacting 6-bromo-1-hexene with excessive sodium azide to obtain 6-azido-1-hexene; 1 molar equivalent of propargyl acrylate and 1 molar equivalent of 6-azido-1-hexene were reacted in cyclohexanone at 90 ℃ for 3 hours to obtain the diolefin compound (a). 10g of 9-anthracenemethanol was dissolved in 100 ml of pyridine solvent, cooled in an ice bath under an inert atmosphere, and then 50ml of undecylenoyl chloride was added thereto, and the mixture was stirred overnight at room temperature to obtain an anthracene derivative (b). Cyanuric acid and 6-chloro-1-hexene are used as raw materials, an olefin compound containing a hydrogen bond group is obtained through reaction under the catalysis of potassium carbonate, and then the olefin compound and methyl hydrogen-containing silicone oil with the molecular weight of 20,000 are subjected to hydrosilylation under the catalysis of Pt to obtain the hydrogen bond group modified silicone oil (c).

Adding 50ml of methyl mercapto silicone oil with the molecular weight of about 30,000 into a three-neck flask, heating to 80 ℃, uniformly stirring, adding 0.01 wt% of BHT antioxidant, 2g of diene compound (a), 0.78g of 1, 11-dibromo-undecane, 4g of anthracene derivative (b) and 0.2 wt% of photoinitiator DMPA, mixing and stirring for 1h, then adding 10ml of hydrogen bond group modified silicone oil (c), uniformly mixing, pouring the polymer into a proper mold, irradiating for 2h by 365nm ultraviolet light under nitrogen atmosphere, and then standing for 30min at room temperature to finally obtain a polymer sample with soft surface and certain viscosity. The polymer material has low surface strength, can be extended to a greater extent under the action of external force, represents excellent tensile toughness, and can be bonded again after being placed in a vacuum oven at 80 ℃ for 2-4h or placed under the illumination condition of certain frequency, thereby representing the self-repairing property based on environmental response.

Example 6

Mixing mercaptoethanol and 3-chloro-2-chloromethyl-1-propylene at a molar ratio of 2:1 by taking methanol as a solvent and sodium methoxide as a catalyst, and reacting for 16h under heating to obtain a diol compound (b) containing an allyl sulfide group. The 1- (6-aminohexyl) -3-ethylurea is prepared by using hexamethylene diamine and ethyl isocyanate with equal molar weight as raw materials.

Weighing 5mmol of polybutadiene epoxy resin (c) with the molecular weight of about 2,000, adding the polybutadiene epoxy resin (c) into a three-neck flask, heating to 80 ℃, introducing nitrogen for 1h, adding a proper amount of triethylamine, slowly adding 0.02mol of bis (2-hydroxy) ethyl tetrasulfide (a), 0.02mol of diol compound (b) containing allyl sulfide group and 0.02mol of 1- (6-aminohexyl) -3-ethylurea under stirring for reaction for 2h, adding a small amount of photoinitiator DMPA, mixing and stirring for 1h, placing a polymer sample into a proper mold, placing the polymer sample into a vacuum oven for drying for 24h, and then cooling to room temperature to finally obtain the epoxy resin elastomer with temperature response characteristics, wherein the epoxy resin elastomer has good electric insulation property, weather resistance and ductility. In the present embodiment, the functional properties exhibited by the polymer material can be utilized for use as an insulating article for electronic and electrical appliances.

Example 7

Weighing 30g of polybutadiene rubber (a), adding the polybutadiene rubber (a) into a small internal mixer, mixing for 20min, adding 3.0g of foaming agent AC, 1.5g of dimercapto compound (b), 1.0g of N- [ (2-mercaptoethyl) carbamoyl ] propionamide, 0.12g of photoinitiator DMPA, 0.08g of ruthenium-based catalyst 1, 1.5g of zinc stearate, 1.5g of tribasic lead sulfate, 2g of white carbon black, 0.05g of barium stearate, 0.1g of stearic acid, 0.1g of antioxidant 168 and 0.2g of antioxidant 1010, continuously mixing for 20min, taking out the mixed material, cooling, placing the mixed material into a double-roll machine to prepare a sheet, cooling at room temperature, cutting into pieces, taking out the prepared polymer sheet, reacting for 15min under ultraviolet irradiation, placing the sheet into a vacuum oven at 80 ℃ for 4h to further react and dry, then cooling to room temperature, placing the mixed sheet into a proper mold, placing the proper mold into a flat vulcanizing machine to perform molding, wherein the temperature is 150 mm, the pore size of the mold pressing, the mold foaming property is 140 min, the mold pressure distribution of the rubber is 20.83-84 mm, the compressive property of the rubber is measured by a universal compression testing machine, the compression strength of the rubber is measured by the compression test of a compression test piece, the compression test piece is 0.2 mm, the compression test piece is 0.83-compression test piece.

Example 8

Adding 20g of polyisoprene (b) and 2.5g of dinitrocarbene compound (a) into a dry and clean reaction bottle, adding 2g of gallium-indium liquid alloy, 0.2g of talcum powder, 0.1g of dibutyltin dilaurate and 0.5g of anhydrous sodium sulfate, heating to 80 ℃, stirring for reaction for 2 hours, adding 5.22g of toluene diisocyanate, quickly mixing, adding 0.05g of ruthenium-based catalyst 1, pouring into a proper mold, placing at 80 ℃ for continuous reaction for 2 hours, cooling to room temperature, and placing for 30 minutes to finally obtain the heat-conducting polyisoprene elastomer material with good tensile toughness and flexibility.

Example 9

Limonene oxide is extracted from orange peel, the limonene oxide and carbon dioxide are subjected to polymerization reaction under the catalysis of β -zinc diimine to obtain polycarbonate PLimC, and then the polycarbonate PLimC and quantitative 3-mercaptoindole are subjected to thiol-ene click reaction to obtain a polycarbonate compound (a).

Pouring a certain amount of chloroform solvent into a dry clean flask, then adding 5mmol of polycarbonate compound (a), introducing nitrogen to remove water and remove oxygen for 1h, then 4mg of BHT antioxidant, 0.04mol of triazolinedione compound (b), 2mmol of diphenyl carbonate, 0.01mol of zinc acetate and 0.01mol of triethylamine are added, heated to 60 ℃ and stirred to be dissolved, then 5 wt% of glass microfiber and 0.3 wt% of sodium dodecyl benzene sulfonate are added, continuing to react for 4 hours under the protection of nitrogen, then placing the mixed solution in a proper mould and drying in a vacuum oven at 50 ℃ for 24 hours to finally obtain transparent hard polymer solid, wherein the polymer solid is hard in texture and has higher mechanical strength and surface hardness, after scratching on the surface of the polymer solid by a blade, the sample is placed in a vacuum oven at 80 ℃ for 4-5h, the scratch can be self-repaired, and the sample can be made into an instrument panel or a recyclable container bottle with self-repairing performance for use.

Example 10

Equimolar amounts of 2-amino-4 (1H) -pyrimidinone and 1, 6-hexamethylene diisocyanate were reacted at 100 ℃ to give compound (a). The maleimide-pyrimidone compound is obtained by reacting an equimolar amount of the compound (a) with an equimolar amount of N-hydroxymaleimide.

Reacting 9-anthracenecarboxylic acid with thionyl chloride to prepare 9-anthraceneacyl chloride; trimethylolpropane and epoxypropane are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, hydroxyl-terminated three-arm polypropylene oxide is synthesized through cationic ring-opening polymerization, and then 1 molar equivalent of hydroxyl-terminated three-arm polypropylene oxide reacts with 1 molar equivalent of compound (a) and 2 molar equivalents of 9-anthracenyl chloride to prepare pyrimidone and anthracene-terminated three-arm polypropylene oxide.

Weighing a certain amount of tetrahydrofuran solvent in a dry and clean reaction bottle, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.04mol of pyrimidone, anthracene-terminated three-arm polypropylene oxide and 0.04mol of maleimide-pyrimidone compound, stirring and dissolving completely, adding a small amount of stannic chloride, carrying out reflux reaction for 12h under the condition of nitrogen protection, then pouring the reaction solution into a proper mould, placing in a vacuum oven at 60 ℃ for 12h for further reaction and drying, then irradiating for 30min by using 365nm ultraviolet light, then cooling to room temperature and placing for 30min, and finally obtaining a colloidal polymer sample. The polymer samples had a low surface hardness and were ductile to external forces. During use, the dynamic covalent bonds contained in the system may exhibit a synergistic effect with changes in ambient temperature and applied ultraviolet light frequency. In this embodiment, the polymer product can be used as a sealant for building caulking or sealing treatment of electronic components.

Example 11

Adding 0.04mol of polyoxypropylene triol into a certain amount of NMP solvent in a dry and clean reaction bottle, heating to 60 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.02mol of 1,3, 5-benzenetricarboxylic acid, and reacting for 24h under the protection of nitrogen to form a first network; and then 0.03mol of polyetheramine D2,000 and 6mmol of paraformaldehyde is added, the mixture is heated to 50 ℃ under the stirring state to react for 30min, and finally the polyether-based organogel with a double-network structure is obtained, the polymer gel has larger surface viscosity and certain resilience, the polymer gel is cut by a blade and then is placed in a solution with certain pH value, complete healing can be realized, excellent self-repairing performance is embodied, the network structure of the gel can be degraded to different degrees under the heating and acidic conditions, and the gel has potential application in the aspects of bioseparation, drug controlled release, sensors and the like by utilizing the self-repairing performance and the temperature/pH responsiveness of the gel.

Example 12

Adding 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine into a mixed solution of styrene and benzoyl peroxide, heating to 90 ℃ under the protection of nitrogen, and reacting for 20 hours to obtain a compound (a), wherein the molar ratio of the benzoyl peroxide to the 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine is 1: 2; and adding the ethanol solution dissolved with the compound (a) into a KOH aqueous solution, and carrying out reflux reaction for 16h under the protection of nitrogen to obtain the dihydroxy compound (b).

A certain amount of toluene solvent is weighed in a reaction bottle, 5mmol of polycaprolactone diol with the molecular weight of about 2,000, 0.01mol of dihydroxy compound (b) and 0.01mol of hydroxyethyl hexahydro-s-triazine (c) are added, the mixture is stirred and mixed uniformly, heated to 80 ℃ to remove water for 1h, then 0.03mol of hexamethylene diisocyanate is added, the mixture reacts for 6h under the protection of nitrogen at 80 ℃, after the reaction is finished, the mixture is cooled to room temperature to finally obtain the polyurethane-based elastomer, a dumbbell-shaped sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm is prepared, a tensile tester is used for tensile test, the tensile rate is 50mm/min, the tensile strength of the sample is measured to be 6.82 +/-2.00 MPa, the tensile modulus is 15.32 +/-3.56 MPa, and the elongation at break is 828 +/-211%.

Example 13

12g of polyester diol PDA-1000, 1.74g of dinitrocarbene compound (a), 1.56g of N, N-bis (2-hydroxyethyl) cinnamamide (b), 2.0g of dibutyltin dilaurate and 1.0g of organic silicone oil are added into a reactor, mixed and stirred uniformly at room temperature, 8.9g of isophorone diisocyanate (IPDI) is added, reaction is carried out for 1h under the protection of nitrogen, then 1 wt% of barite powder, 2 wt% of gypsum, 1 wt% of carbon black and 0.3 wt% of sodium dodecyl benzene sulfonate are added, and the reaction is continued for 2h after ultrasonic treatment for 20 min. After the reaction is finished, pouring the polymer solution into a proper mould, placing the mould in a vacuum oven at 80 ℃ for 12h to remove the solvent, then placing the mould under 280nm ultraviolet light for irradiation for 30min, then cooling to room temperature and placing the mould for 30min to finally obtain the polymer colloid. In the embodiment, the polymer can be used as an electronic packaging material or an adhesive, in the using process, the synergistic effect can be embodied by utilizing the difference of the responsiveness of different types of dynamic covalent bonds in the polymer to temperature and illumination conditions, the polymer can be recycled, and the polymer sample has a long service life.

Example 14

Weighing 5g of 9-anthracene formaldehyde in a dry and clean reaction bottle, adding 100ml of THF solvent, stirring and dissolving completely under the nitrogen atmosphere, irradiating by using 300nm ultraviolet light for 20h, filtering and washing precipitate by using THF, and placing in a vacuum oven to remove the solvent to finally obtain the 9-anthracene formaldehyde dimer (a). Equimolar 2-amino-4 (1H) -pyrimidone and 1, 6-hexamethylene diisocyanate are reacted at 100 ℃ to prepare a compound (b), and then the compound (b) is reacted with polyvinyl alcohol to prepare a polyvinyl alcohol compound containing partial side hydrogen bond groups.

Adding 10g of polyvinyl alcohol compound containing partial side hydrogen bond groups, 2.06g of 9-anthracene formaldehyde dimer (a) and 1.8g of paratoluenesulfonic acid monohydrate into a dry and clean reaction bottle, adding 150ml of deionized water into the reaction bottle, placing the reaction bottle in a water bath kettle at 60-70 ℃, continuously stirring to uniformly stir the mixed solution, adding 3g of carbon nano tube and 0.3g of sodium dodecyl benzene sulfonate, continuously stirring for 30min, adding 0.08g of bentonite, continuously stirring and mixing at 60 ℃ for reaction for 24h, pouring the reaction solution into a proper mold, placing the mold in a vacuum oven at 80 ℃ for drying to remove the solvent for 24h, cooling to room temperature for 30min, finally obtaining a polymer colloid dispersed with conductive fillers, wherein the polymer colloid has good rebound resilience and surface viscosity, can be stretched and expanded, making a 20.0 × 20.0.0 20.0 × 20.0.0 mm-size sample, performing a compression performance test by using a universal testing machine, measuring the compression rate to be 2mm/min, measuring the compression strength of the sample to be 0.64 +/-0.20.20 mm, cutting the sample into a block-shaped polymer, and placing the block-shaped polymer colloid in the adhesive capable of being used as a self-repairing material after the photo-adhesive gel is cut, and the sample is used for bonding the block-shaped polymer gel.

Example 15

Adding 0.1mol of diethanolamine and a certain amount of anhydrous methanol into a dry three-neck flask, uniformly stirring at room temperature, adding 0.2mol of methyl acrylate, stirring at 35 ℃ for 4h, vacuumizing to remove excessive methanol and methyl acrylate, reacting the mixture with trimethylolpropane in a dropwise manner at 115 ℃ under the catalysis of p-toluenesulfonic acid to obtain a primary intermediate product, reacting the primary intermediate product with 3- (bis (2-hydroxyethyl) amino) methyl propionate to obtain a secondary intermediate product, and blocking by using 3-propylene isocyanate to obtain the hyperbranched compound (a).

Dimethyl formamide (DMF) is taken as a solvent, the molar ratio of 4-chloro-1-butene to sodium diselenide is controlled to be 2:1, and the reaction is carried out for 24 hours at 22 ℃ under the protection of nitrogen to obtain the diene compound (b) containing the diselenide bond.

Adding 0.01mol of hyperbranched compound (a) into a dry and clean reaction bottle, adding a certain amount of chloroform solvent for dissolving, introducing nitrogen to remove water and remove oxygen for 1h, adding 0.3 wt% of AIBN and 1.0 wt% of triethylamine, sequentially and slowly adding 0.02mol of diene compound (b), 0.03mol of trithiol compound (c) and 9mmol of 4-bromobenzenesulfonic acid butyl ester (d), and continuously reacting for 6h under the condition of nitrogen protection at 60 ℃. And then pouring the polymer solution into a proper mould, placing the mould in a vacuum oven at 50 ℃ for 12h for drying, and finally obtaining a transparent film with certain flexibility, wherein the transparent film is soft in texture, has certain tensile strength and good tensile toughness, and can be placed in a mould at 120 ℃ or self-repaired by ultraviolet irradiation when the transparent film is damaged, so that the reutilization is realized.

Example 16

Reacting 6-bromo-1-hexene with excessive sodium azide to obtain 6-azido-1-hexene; 1 molar equivalent of propargyl acrylate and 1 molar equivalent of 6-azido-1-hexene were reacted in cyclohexanone at 90 ℃ for 3 hours to obtain the diolefin compound (a).

Equimolar amounts of 1, 4-pentadiene-3-ol and cyclohexyl isocyanate were used as starting materials, and 1 wt% dibutyltin dilaurate was used as a catalyst, and reacted in a methylene chloride solvent to obtain a diene compound (b) having a pendant carbamate group.

Weighing 0.02mol of a diene compound (a), 0.02mol of a diene compound (b), 0.02mol of 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine (c), 0.07mol of 1, 10-decanedithiol and 0.02mol of 1, 11-dibromoundecane, uniformly mixing, adding 0.2 wt% of benzoin dimethyl ether (DMPA) as a photoinitiator, adding 1 wt% of metal osmium heteroaromatic ring particles and 1 wt% of nano silver particles, fully stirring uniformly, placing in an ultraviolet cross-linking instrument for ultraviolet radiation for 4h to obtain a dynamic polymer cross-linked network containing a skeleton hydrogen bond and a side hydrogen bond, wherein the obtained polymer sample has good resilience and certain tensile toughness, after cracks or damages appear on the surface of the polymer material, placing in a vacuum oven at 60 ℃ for 3h, scratching disappears, cutting off the polymer sample, after the sample is placed in a vacuum oven at 120 ℃ for 4 hours, the sample can be bonded again and can generate heat under the action of infrared rays, and the obtained polymer sample can be used for manufacturing heat-conducting gaskets and is applied to the fields of automobile industry and various mechanical devices.

Example 17

Adding 300ml of xylene solvent into a dry and clean three-neck flask, adding 3.3g of 3,3' -diselenodipropionic acid, 3.4g of 1, 4-butanediol, 3.42g of butynedioic acid, 2.58g of butynediol, 12g of hydroxyl-terminated polybutadiene and a proper amount of stannous chloride catalyst, heating to 160 ℃ to perform esterification reaction, timely removing water through xylene, raising the temperature to 220 ℃ to perform polymerization reaction when the water yield is about 80% of the theory, then adding a ruthenium-based catalyst 10, continuing to react for a while, pouring viscous reaction liquid into a proper mold, placing the mold into a vacuum oven at 80 ℃ for 24 hours to perform further reaction, then cooling to room temperature and placing for 30 minutes to finally obtain a rubbery polymer sample. In the embodiment, the dynamically crosslinked polymer material has good extensibility and self-repairing performance, can achieve the capability of coordination and orthogonal regulation by utilizing the difference of dynamic covalent bonds and hydrogen bond dynamics under the heating condition, embodies the self-repairing effect and tensile toughness of different degrees, and can be used as a functional sealant or plugging adhesive.

Example 18

Taking the compound (a) as a raw material, and carrying out Diels-Alder reaction on the compound (a) and N- (2-hydroxyethyl) maleimide to prepare a hydroxyl-terminated maleimide-furan compound (b).

Adding 10g of polypropylene oxide glycol into a dry and clean reaction bottle, heating to 110 ℃ to remove water for 1h, then adding 3.2g N, N-bis (2-hydroxyethyl) -9-anthracene benzylamine (c), 3.0g of hydroxyl-terminated maleimide-furan compound (b), 16.7g of diphenylmethane diisocyanate, 10g of acetone and 0.4g of stannous octoate, reacting for 3h under the condition of 80 ℃ nitrogen protection, after the reaction is finished, removing the acetone in vacuum, cooling to room temperature to obtain a polyurethane sample with good resilience, placing the polyurethane sample under the condition of 350nm ultraviolet illumination for curing reaction for 2h to obtain a final polymer sample, preparing the final polymer sample into a sample strip with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, performing tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 4.32 +/-1.05 MPa, the tensile modulus is 10.56 +/-2.88 MPa, the elongation at break is 712 +/-150%, the resilience of the dumbbell material is good, the toughness of the sample, the self-repairing polyurethane material can achieve the self-repairing effect by using different compressive cracks under the self-repairing effect.

Example 19

The compound (a) is prepared by using AIBN as an initiator and triethylamine as a catalyst and sequentially carrying out thiol-alkene click addition reaction on 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine and quantitative 1-mercaptopropan-2-ol.

100ml of epoxidized soybean oil is poured into a dry clean flask, nitrogen is introduced to remove water and oxygen for 1h, 4g of polytetrahydrofuran diol with the molecular weight of about 1,000 is added, 1.2g of a compound (a), 1.36g of N, N '-di-tert-butyl hexanediamine (b), 1.18g N, N' -tri-tert-butyl-tris (3-aminoethyl) amine (c) and 5.04g of decane-1, 10-diisocyanate are added, the mixture is heated to 80 ℃ under the protection of nitrogen and stirred for reaction for 30min, 2.8g of metal osmium heteroaromatic ring particles, 2.8g of nano silver particles and 0.08g of bentonite are added, the mixture is continuously stirred and mixed under the protection of nitrogen at 80 ℃, after the reaction is finished, a heat-conducting polymer elastomer with good resilience can be obtained, and the polyurethane heat-conducting adhesive with heat-conducting characteristics can be prepared.

Example 20

And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polypropylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polypropylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10.

17.8g of 2- (ethylamino) ethanol and 100mL of chloroform are added into a reaction flask, and under the ice-bath condition, 6mL of carbon disulfide and 12.7g of iodine are added, and after reaction for 3 hours, dihydroxy thiuram disulfide (a) is obtained through purification.

20g of maleic anhydride grafted polypropylene, 1.05g of methyl (hydroxymethyl) -carbamate, 1.25g of dihydroxy thiuram disulfide (a), 1.5g of 2-hydroxychalcone and 10mg of BHT antioxidant are added into a dry and clean three-neck flask, heated to 160 ℃ under the protection of nitrogen, melted, stirred and mixed for 1h, then 0.25g of p-toluenesulfonic acid, 3.0g of plasticizer DOP and 0.5g of dimethyl silicone oil are added, and the reaction is continued for 3h under the protection of nitrogen. And then pouring the polypropylene-based polymer into a proper mould, carrying out compression molding at 120 ℃ by using a molding press, cooling to room temperature, standing for 30min, and carrying out ultraviolet irradiation curing for 2h by 280nm to finally obtain a polypropylene-based polymer sample. It is made into

80.0 × 10.0.0 10.0 × (2.0-4.0) mm dumbbell-shaped sample strips are subjected to a tensile test by a tensile testing machine, the tensile rate is 50mm/min, the tensile strength of the sample is 5.98 +/-1.88 MPa, the tensile modulus is 14.12 +/-3.25 MPa, and the elongation at break is 714 +/-205%.

Example 21

Using equal molar weight of acryloyl chloride and 7- (2-hydroxyethoxy) coumarin as raw materials, and reacting under the action of triethylamine to obtain the coumarin-containing acrylate compound (a). The acrylate copolymer (c) is obtained by radical polymerization of an acrylate compound (a) containing coumarin and methyl methacrylate using AIBN as an initiator.

Hydroxyethyl acrylate and 3,3' -trithiocarbonate dipropionate are taken as raw materials, the molar ratio of the hydroxyethyl acrylate to the trithiocarbonate is controlled to be 2:1, and the diene compound (b) containing trithiocarbonate is synthesized.

Reacting isocyanate ethyl acrylate with ethylamine to prepare an acrylate monomer containing a urea bond; and (d) carrying out free radical polymerization on the acrylate monomer containing the urea bond and methyl methacrylate by using AIBN as an initiator to obtain the acrylate copolymer (d).

Adding 200ml of toluene solvent into a dry and clean reaction bottle, introducing argon to remove water and oxygen for 1h, adding 8g of methyl methacrylate, 1.5g of diene compound (b) containing trithiocarbonate and 1.2 wt% of AIBN, heating to 80 ℃ under the protection of argon, and reacting for 5h to form a first network; then 6g of acrylate copolymer (c) and 5.5g of acrylate copolymer (d) are added, the mixture is continuously stirred and reacts for 2 hours, then 1 wt% of barite powder, 2 wt% of gypsum, 1 wt% of carbon black, 0.3 wt% of sodium dodecyl benzene sulfonate and 0.2 wt% of photoinitiator DMPA are added, and the mixture is subjected to ultrasonic treatment for 20 minutes and then continuously reacts for 2 hours. After the reaction is finished, pouring the polymer solution into a proper mould, placing the mould in a vacuum oven at 80 ℃ for 12h to remove the solvent, then placing the mould under ultraviolet light of 350nm for irradiation for 30min, then cooling to room temperature and placing the mould for 30min to finally obtain the polymer solid with certain surface glossiness, surface strength and surface hardness, reheating or illuminating the polymer solid after scratching on the surface of the polymer solid, wherein the scratches can be self-repaired, and the polymer solid can be made into an artistic molding with good moldability and self-repairing capability.

Example 22

1- (3-hydroxypropyl) -3, 6-dimethyl pyrimidine-2, 4-diketone and acryloyl chloride are used as raw materials to react to prepare the acrylic pyrimidone (a). Taking AIBN as an initiator, and carrying out free radical polymerization on acrylamide and acrylic pyrimidone (a) to obtain a pyrimidone-acrylamide copolymer. And (2) carrying out free radical polymerization on acrylamide and 2-aminoethyl methacrylate by using AIBN as an initiator to obtain the amino modified acrylamide copolymer.

10g of amino-modified acrylamide copolymer are weighed into a dry, clean beaker, and 100ml of deionized water are added thereto, during which stirring is continuedDissolving the mixture completely, adding 0.75g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, and carrying out reflux reaction for 2 hours at 65 ℃ under the protection of nitrogen to form a first network polymer; then 10g of pyrimidone-acrylamide copolymer is added, the mixture is continuously stirred and dissolved at 50 ℃, and after the mixture is completely dissolved, 5 wt% of surface modified Fe is added₃O₄And (2) carrying out ultrasonic treatment on the particles, 5 wt% of metal magnetic powder and 1 wt% of bentonite for 1min to uniformly disperse the metal particles in the particles, then placing the particles in a constant-temperature water bath at 60 ℃ to react for 1h, continuously increasing the viscosity of the solution along with the reaction, heating the solution to react for 2h to obtain a viscous polymer sample, and placing the viscous polymer sample under 350nm ultraviolet light to irradiate for 2 h. After the reaction is finished, the double-network hydrogel dispersed with the magnetic particles is obtained. In this embodiment, the obtained polymer magnetic gel can be used as an intelligent gel material with magnetic field responsiveness, and based on the orthogonality control capability of different types of dynamic covalent bonds, multiple responses to the gel material can be realized through multiple means such as heating, illumination, pH adjustment and the like.

Example 23

Weighing 3g of terephthalaldehyde, dissolving in 50ml of absolute ethanol, adding 8.9g of diethyl malonate, 0.2g of piperidine and 0.2g of acetic acid, carrying out reflux reaction for 12 hours under the argon atmosphere, and then cooling and purifying to obtain the compound (a).

Isocyanate ethyl acrylate and 2-aminopyridine are used as raw materials to react to prepare a monomer containing carbamido; AIBN is used as an initiator, hydroxyethyl acrylate, 2-aminoethyl acrylate, vinyl pyrrolidone and a monomer containing urea are used as raw materials, and the vinyl pyrrolidone copolymer is obtained through free radical polymerization.

200ml of deionized water is weighed in a dry and clean three-neck flask, 10g of vinyl pyrrolidone copolymer, 0.89g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid are added, after complete stirring and dissolution, reflux reaction is carried out at 65 ℃ under the protection of nitrogen, after a polymer solution has certain viscosity, 6.0g of compound (a) and 4.8g of triethylenetetramine are added, stirring is carried out uniformly, the mixture is heated to 50 ℃ to continue to react for 10 hours, and after the reaction is finished, the hybrid cross-linked double-network hydrogel is obtained. In this example, the resulting polymeric hydrogel can be used as a liquid-absorbent liner material having both superabsorbent and pH-responsive properties, which can achieve self-healing and recycling of the gel under heat or different pH conditions.

Example 24

The 1- (6-aminohexyl) -3-ethylurea is prepared by taking hexamethylene diamine and ethyl isocyanate with equal molar weight as raw materials to react; the modified ethylene propylene rubber is prepared by taking low molecular weight ethylene propylene rubber as a raw material, reacting by using dibenzoyl peroxide as a cross-linking agent to form a small cluster structure, grafting maleic anhydride on the surface of the cluster, and reacting with 1- (6-aminohexyl) -3-ethylurea by using p-toluenesulfonic acid as a catalyst.

Weighing 7.2g of modified ethylene propylene rubber, adding the modified ethylene propylene rubber into a dry clean beaker, pouring 80ml of xylene solvent, heating and stirring, adding 0.82 g of 2,2' -diselenodiethanol (a) and 0.6g of N-aminoethyl-S-aminoethyl dithiocarbamate (b), continuously stirring and mixing for 30min, adding 1.0mg of BHT antioxidant, 0.02g of photoinitiator DMPA and 1ml of triethylamine, continuously reacting for 3h at 80 ℃ to obtain viscous polymer liquid, placing the viscous polymer liquid in a proper mold, placing the viscous polymer liquid in a vacuum oven at 80 ℃ for 24h to remove the solvent, cooling to room temperature, placing for 30min, taking out a sample from the mold to finally obtain a rubber-like dynamic polymer, preparing a dumbbell-shaped sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, performing a tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 3.12 +/-0.98 MPa, the tensile modulus is 7.50 +/-1.88 MPa, the elongation rate can reach 152%, the breakage rate of the sample can be reached, the sample can be recovered by using a good heat-resistant and the good-resistant and hydrolysis, the sample can be recovered.

Example 25

Preparing a hydroxyl double-terminated compound by taking AIBN as an initiator and triethylamine as a catalyst and carrying out a thiol-ene click reaction on 1, 4-butylene glycol and N- [ (2-mercaptoethyl) carbamoyl ] propionamide in equimolar amount; then DCC and DMAP are used as condensation reagents, and are subjected to esterification reaction with acrylic acid to prepare an olefin double-terminated compound; and then taking AIBN as an initiator and triethylamine as a catalyst, and carrying out thiol-ene click addition reaction on the AIBN and 2-hydroxyethyl-3-mercaptopropionate to obtain the hydroxyl compound (a).

Adding 20ml of end aldehyde polyethylene glycol 2,000, 2.2g of hydroxyl compound (a) and 0.2mg of antioxidant BHT into a dry and clean three-neck flask, dropwise adding 0.5ml of p-toluenesulfonic acid, heating to 65 ℃, stirring for reaction, cooling to room temperature after reaction for 5 hours to obtain a light yellow transparent viscous sample, dissolving a small amount of polymer in toluene to prepare a solution of 10mg/ml, wherein the solution can show different self-repairing capabilities under the conditions of heating and different pH values.

Example 26

1, 6-hexamethylene diisocyanate and furfuryl alcohol are used as raw materials, dichloromethane is used as a solvent, stannous octoate is used as a catalyst, the molar ratio of the raw materials to the dichloromethane is controlled to be 1:2, the reaction is carried out for 2 hours at room temperature under the protection of nitrogen, and the reflux reaction is carried out for 2 hours to prepare a difuran compound (b).

15g of polytetrahydrofuran diol, 1.74g of dinitrocarbene compound (a), 2.05g N- (3, 4-dihydroxyphenyl) maleimide, 2.0g of dibutyltin dilaurate and 1.0g of organic silicone oil are added into a reactor, mixed and stirred uniformly at room temperature, 10.44g of toluene diisocyanate is added, reaction is carried out for 1h under the protection of nitrogen, then 3.25g of the tetrahydrofuran compound (b), 5 wt% of silicon dioxide, 5 wt% of barium sulfate, 0.02 wt% of sodium dodecyl benzene sulfonate and 0.02 wt% of bentonite are added, and the stirring reaction is continued for 1h, so as to obtain a viscous polymer sample. Due to the fact that different types of dynamic covalent bonds exist in the polymer material in the embodiment, different self-repairing effects can be achieved under the conditions of normal temperature and heating conditions based on the fact that the polymer material is different in dynamic property under different temperature conditions, and orthogonality is achieved.

Example 27

2,2,6, 6-tetramethyl-4-piperidyl methacrylate and adipoyl chloride are used as raw materials, the molar ratio of the raw materials to the adipoyl chloride is controlled to be 2:1, and the acrylate end-capped compound is prepared.

Adding 50ml of liquid paraffin and 10ml of methyl hydrogen silicone oil (the molecular weight is about 3,000) into a dry and clean three-neck flask in sequence, introducing nitrogen to remove water and oxygen for 20min, adding 5.34g of acrylate end-capping compound and 2ml of 1% Pt (dvs) -THF solution as a catalyst, reacting for 24h under the protection of nitrogen, adding 3 wt% of tetramethylammonium hydroxide and 2 wt% of sodium glycerol, and continuing to react for 6h to finally obtain the polymer colloid with certain viscoelasticity. The polymer elastomer has lower surface strength, good ductility and moisture resistance, and can be made into a toy with a viscosity-elasticity magic conversion effect.

Example 28

Adding 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine into a mixed solution of styrene and benzoyl peroxide, heating to 90 ℃ under the protection of nitrogen, and reacting for 20 hours to obtain a compound (a), wherein the molar ratio of the benzoyl peroxide to the 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine is 1: 2; adding an ethanol solution in which the compound (a) is dissolved into a KOH aqueous solution, carrying out reflux reaction for 16h under the protection of nitrogen to obtain a compound (b), dissolving the compound (b) and methacryloyl chloride in an anhydrous tetrahydrofuran solvent, and carrying out reaction for 10h under the protection of argon at room temperature to obtain a compound (c). Acrylic acid 2-aminoethyl ester and ethoxycarbonyl isocyanate are catalyzed by triethylamine to obtain an acrylate monomer containing a hydrogen bond group, and then AIBN is used as an initiator to copolymerize with styrene through free radicals to obtain the hydrogen bond group modified polystyrene (e). Benzoyl peroxide is used as an initiator, and styrene and 4-vinylpyridine are subjected to free radical copolymerization to prepare the styrene-pyridine copolymer.

Adding a certain amount of toluene solvent into a dry and clean reaction bottle, removing water and oxygen by introducing argon gas for 1h, adding 8g of styrene, 2.0g of compound (c), 0.8 wt% of benzoyl peroxide and 0.2 wt% of photoinitiator DMPA, heating to 80 ℃ under the protection of argon gas for reaction for 4h, adding 5g of styrene-pyridine copolymer and 0.61g of phenyl selenium bromide (d), continuously stirring and mixing for 1h, adding 8g of hydrogen bond group modified polystyrene (e), continuously reacting for 20h under the atmosphere of argon gas, placing the mixed solution into a proper mould, drying in a vacuum oven at 80 ℃ for 24h, finally obtaining a hard polystyrene-based polymer material which has certain surface glossiness and surface hardness, after scratching the surface of the hard polystyrene-based polymer material by using a blade, placing a sample in the vacuum oven at 80 ℃ for 4-5h to realize self-repairing, it can be made into rigid packaging box with self-repairing property, or optical instrument shell.

Example 29

Weighing 30g of styrene-maleic anhydride copolymer, 1.6g of 1- (6-aminohexyl) -3-ethylurea, 1.5g of N-aminoethyl-S-aminoethyl dithiocarbamate (b), 1.8g of 2,2' -dithiodiethanol, 0.15g of p-toluenesulfonic acid, 1.4g of di-N-butyltin dilaurate, 4.2g of dioctyl phthalate, 4g of foaming agent F141b, 0.2g of photoinitiator DMPA, 0.2g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010, uniformly mixing, adding into a small internal mixer for banburying and blending, controlling the mixing temperature to be below 40 ℃, taking out the sample after mixing, filling into a compression mold, closing the mold for pressurizing and heating, wherein the mold pressing temperature is 100-110 ℃, the mold pressing time is 10-15min, the pressure is 10MPa, placing the demolded pre-foamed blank into a vacuum oven at 100 ℃ for further reaction and drying, finally obtaining a polystyrene-based foamed sample, preparing the foamed sample into a universal foamed material with the foamed material of which the specific gravity is 20.32 mm, the foamed material is obtained by a compression test, and the foamed material is subjected to a compression test process of a compression test speed of a compression tester, wherein the foamed material is 20.32 mm, the foamed material is subjected to obtain a foamed material, and the foamed material is subjected to a size of a compression tester, and a compression tester is subjected to be.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. A composite hybrid dynamic polymer comprising at least two crosslinked networks, wherein the crosslinked networks comprise at least two types of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

2. The hybrid dynamic polymer of claim 1, wherein the dynamic sulfur linkage is selected from the following structures:

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

the dynamic double selenium bond is selected from the following structures:

the dynamic selenium-nitrogen bond is selected from the following structures:

wherein X is selected from halide ions;

the acetal dynamic covalent bond is selected from at least one of the following structures:

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

the dynamic covalent bond based on carbon-nitrogen double bond is selected from at least one of the following structures:

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

the dynamic covalent bond based on the reversible free radical is selected from at least one of the following structures:

wherein, X₁、X₂Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C_3-20Alkyl, divalent or polyvalent cyclic C_3-20Alkyl, phenyl, benzyl, aromatic, carbonyl, sulfone, phosphate, and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; wherein each W is independently selected from an oxygen atom, a sulfur atom; w₁Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups, and substituents thereof; w₂Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof; w₃Each independently selected from ether groups, thioether groups; w₄Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a divalent methyl group and substituents thereof; w, W at different locations₁、W₂、W₃、W₄The structures of (A) are the same or different; wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R at different positions₁The same or different; wherein R is₂Each independently selected from hydrogen atom, cyano group, hydroxy group, phenyl group, phenoxy group, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein L ' is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, a divalent small molecule hydrocarbon group, and L ' at different positions 'The same or different; wherein V, V ' are each independently selected from carbon atom, nitrogen atom, V, V ' at different positions are the same or different, and when V, V ' is selected from nitrogen atom, it is connected to V, V

Is absent; wherein,

the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms;

the binding exchangeable acyl bond is selected from at least one of the following structures:

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

the dynamic covalent bond based on steric effect induction is selected from at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, silicon atoms and nitrogen atoms; z₁、Z₂Selected from oxygen atoms and sulfur atoms; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R is_bIs a bulky group with steric effect directly connected with nitrogen atom and selected from C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof;

the reversible addition fragmentation chain transfer dynamic covalent bond is selected from at least one of the following structures:

wherein R is₁～R₁₀Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x₁、X₂、X₃Each independently selected from single bond, divalent or polyvalent small molecule alkyl; z₁、Z₂、Z₃Each independently selected from single bonds, heteroatom linking groups, divalent or polyvalent small molecule hydrocarbon groups;

the dynamic siloxane bond is selected from the following structures:

the dynamic silicon ether bond is selected from the following structures:

the alkyl triazolium-based exchangeable dynamic covalent bond is selected from the following structures:

wherein, X^—Is negative ion selected from bromide ion and iodide ion;

the unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction is selected from the following structures:

the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction is selected from the following structures:

the [2+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

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

The [4+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

wherein, K₁、K₂、K₅～K₁₀Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₅、K₆Or K₇、K₈Or K₉、K₁₀At least one atom selected from carbon atom or nitrogen atom; c. C₁～c₁₀Respectively represent and K₁～K₁₀The number of connected connections; when K is₁、K₂、K₅～K₁₀Each independently selected from an oxygen atom and a sulfur atom, c₁、c₂、c₅～c₁₀0; when K is₁、K₂、K₅～K₁₀Each independently selected from nitrogen atoms, c₁、c₂、c₅～c₁₀1 is ═ 1; when K is₁、K₂、K₅～K₁₀Each independently selected from carbon atoms, c₁、c₂、c₅～c₁₀＝2；K₃、K₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C₃、c₄Respectively represent and K₃、K₄The number of connected connections; when K is₃、K₄Each independently selected from an oxygen atom and a sulfur atom, c₃、c₄0; when K is₃、K₄Each independently selected from nitrogen atoms, c₃、c₄＝1；I₁、I₂Each independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule alkyl;

the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;

the [4+4] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

wherein,

the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms; i is₆～I₁₄Each independently selected from oxygen atom, sulfur atom, amido, ester group, imino, divalent small molecule alkyl;

the dynamic covalent bond of the mercapto-Michael addition is selected from at least one of the following structures:

wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group selected from the group consisting of aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonic acid groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;

the amine alkene-Michael addition dynamic covalent bond is selected from the following structures:

the dynamic covalent bond based on triazolinedione-indole is selected from the following structures:

the dynamic covalent bond based on the diazacarbene is selected from at least one of the following structures:

the hexahydrotriazine dynamic covalent bond is selected from at least one of the following structures:

the dynamically exchangeable trialkylsulfonium linkage is selected from the following structures:

wherein, X^—Selected from the group consisting of sulfonate salts.

3. The combined hybrid dynamic polymer according to claim 1, characterized in that it has one of the following structures:

the first method comprises the following steps: the combined hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds, and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all the crosslinked networks are at least of two types;

and the second method comprises the following steps: the combined hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least two types of dynamic covalent bonds, and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one hydrogen bond, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point;

and the third is that: the combined hybrid dynamic polymer is a double-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bonds and hydrogen bonds, and the cross-linking degree of the two cross-linked networks is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all the crosslinked networks are at least of two types;

and fourthly: the combined hybrid dynamic polymer is a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bond, and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one type of dynamic covalent bond, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; and the dynamic covalent bonds in all the crosslinked networks are at least of two types;

and a fifth mode: the combined hybrid dynamic polymer is a three-network cross-linked structure, wherein one cross-linked network contains at least one type of dynamic covalent bond, and the cross-linking degree of the dynamic covalent bond cross-linking is above the gel point; the other crosslinking network contains at least one type of dynamic covalent bonds, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point; the last crosslinking network contains at least one hydrogen bond, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point; and the dynamic covalent bonds in all crosslinked networks are of at least two types.

4. Combined hybrid dynamic polymer according to claim 3, characterized in that supramolecular polymers with a degree of supramolecular cross-linking below their gel point and/or supramolecular polymer particles with a degree of supramolecular cross-linking above their gel point are dispersed in the combined hybrid dynamic polymer cross-linked network.

5. A composite hybrid dynamic polymer comprising only one crosslinked network containing at least two types of dynamic covalent bonds and optionally hydrogen bonds in the crosslinked network; wherein the dynamic covalent bond is selected from the group consisting of a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a combinable exchangeable acyl bond, a dynamic covalent bond induced based on steric effects, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of undergoing an alkene cross-metathesis reaction, an unsaturated carbon-carbon triple bond capable of undergoing an alkyne cross-metathesis reaction, an amine alkene-michael addition dynamic covalent bond, a triazolinedione-indole based dynamic covalent bond, a dinitrohetero carbene based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a combination of dynamic exchangeable trialkyl sulfonium bonds; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

6. A composite hybrid dynamic polymer, characterized in that it contains only one cross-linked network, and at least two types of dynamic covalent bonds and hydrogen bonds are contained in the cross-linked network; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the hydrogen bond is formed by taking carbamate, carbamide, thiocarbamate, thiourea, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin and derivatives of the above groups as hydrogen bond groups; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

7. The combined hybrid dynamic polymer according to any one of claims 5 and 6, characterized in that it has one of the following structures:

the first method comprises the following steps: the combined hybrid dynamic polymer only contains one cross-linked network, and the cross-linked network contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the crosslinking degree of dynamic covalent bond crosslinking is below the gel point, the crosslinking degree of hydrogen bond crosslinking is below the gel point, and the sum of the crosslinking degrees of the two is above the gel point;

and the second method comprises the following steps: the combined hybrid dynamic polymer only contains one cross-linked network, and the cross-linked network contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the crosslinking degree of dynamic covalent bond crosslinking is below the gel point, and the crosslinking degree of hydrogen bond crosslinking is above the gel point;

and the third is that: the combined hybrid dynamic polymer only contains one cross-linked network, and the cross-linked network contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point, and the crosslinking degree of the hydrogen bond crosslinking is below the gel point;

and fourthly: the combined hybrid dynamic polymer only contains one cross-linked network, and the cross-linked network contains at least two types of dynamic covalent bonds and hydrogen bonds; wherein the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point, and the crosslinking degree of the hydrogen bond crosslinking is above the gel point.

8. The hybrid dynamic polymer according to claim 7, wherein the crosslinked network of the hybrid dynamic polymer comprises supramolecular polymers with a degree of supramolecular crosslinking below their gel point and/or supramolecular polymer particles with a degree of supramolecular crosslinking above their gel point.

9. A composite hybrid dynamic polymer characterized by a non-crosslinked structure containing at least two types of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic selenazon bond, a dynamic covalent bond based on reversible free radicals, a combinable exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis reaction, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis reaction, an amine-Michael addition dynamic covalent bond, a dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on dinitrohetero-carbene, a hexahydrotriazine dynamic covalent bond, and a combination of dynamic exchangeable trialkyl sulfonium bonds; wherein the presence of said dynamic covalent bonds, and optionally hydrogen bonds, is a necessary condition for forming or maintaining the polymer structure.

10. A composite hybrid dynamic polymer, characterized in that it is a non-crosslinked structure containing at least two types of dynamic covalent bonds and hydrogen bonds; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein, the hydrogen bond is formed by carbamido, thiocarbamate, thiourea, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin and derivatives of the above groups as hydrogen bond groups; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

11. A composite hybrid dynamic polymer characterized by being a non-crosslinked structure containing at least two types of dynamic covalent bonds and hydrogen bonds formed by pendant hydrogen bonding groups; wherein the dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, a bonding exchangeable acyl bond, a dynamic covalent bond based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-addition dynamic covalent bond, a, A combination of a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining the polymer structure.

12. The hybrid dynamic polymer of any one of claims 1,6, 10, 11 wherein said dynamic covalent bond is selected from the group consisting of:

13. The combined hybrid dynamic polymer according to any one of claims 1, 5, 6, 9, 10 and 11, wherein the formulation components constituting the combined hybrid dynamic polymer composition comprise any one or more of the following additives/usages: auxiliaries/additives, fillers;

wherein, the auxiliary agent/additive is selected from any one or more of the following components: catalysts, initiators, redox agents, antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, mold release agents, plasticizers, foaming agents, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, and leveling agents;

wherein, the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

14. The combined hybrid dynamic polymer according to any one of claims 1, 5, 6, 9, 10, 11, characterized in that the morphology of the combined hybrid dynamic polymer has any one of the following: solutions, emulsions, gels, pastes, glues, elastomers, common solids, foams.

15. The hybrid dynamic polymer according to any one of claims 1, 5, 6, 9, 10, 11, wherein it is applied to self-healing coatings, self-healing sheet materials, self-healing adhesives, sealing materials, tough materials, energy storage device materials, laminating glues, toys, shape memory materials.