CN108341960B

CN108341960B - Dynamic polymer containing combined dynamic covalent bonds and application thereof

Info

Publication number: CN108341960B
Application number: CN201710055961.6A
Authority: CN
Inventors: 请求不公布姓名
Original assignee: Xiamen Tiance Material Technology Co ltd
Current assignee: Xiamen Iron Cloth Mstar Technology Ltd
Priority date: 2017-01-25
Filing date: 2017-01-25
Publication date: 2023-08-25
Anticipated expiration: 2037-01-25
Also published as: CN108341960A

Abstract

A dynamic polymer containing a combination of dynamic covalent bonds, comprising at least two classes of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is an organoborate bond, which is at least selected from the group consisting of an organoborate ring bond, an organoborate monoester bond, an organoborate silicon bond, and an organoborate anhydride bond; the presence of the dynamic covalent bond as a polymeric and/or cross-linking linkage point of the dynamic polymer is a necessary condition for forming or maintaining the dynamic polymer structure. The dynamic polymer can be used for manufacturing damping buffer materials, impact-resistant protective materials, energy-absorbing materials, coating materials, sound-insulating and silencing materials, intelligent sensing materials, self-repairing materials, toughness materials, force sensors and the like.

Description

Dynamic polymer containing combined dynamic covalent bonds and application thereof

Technical Field

The invention relates to the field of dynamic polymer materials, in particular to a polymer material formed by dynamic reversible covalent bonds.

Background

The covalent dynamic polymer is a brand new field in the research of high molecular science, the dynamic polymer based on dynamic covalent bonds not only has the molecular structure stability of the traditional covalent polymer, but also has the dynamic reversibility of the super molecular polymer under certain conditions, and is a totally new intelligent material. Compared with the non-covalent interaction of supermolecules, the dynamic covalent bond has stronger bond energy and smaller influence of thermal mechanics, and the formed dynamic polymer has a relatively stable molecular structure, and the dynamic covalent bond well combines the reversibility of the non-covalent interaction of the supermolecules and the stability of covalent bonds, thereby playing an important role in the aspects of building functional molecules and materials, developing novel energy-absorbing materials, developing chemical sensors, regulating and controlling biomolecules, controlling intelligent molecular switches and machines and the like.

The types of the dynamic covalent bonds found at present are more and more abundant, and reports on dynamic polymers formed by the dynamic covalent bonds are more and more concentrated, and only one dynamic covalent bond is contained in each dynamic polymer to provide the dynamic property of the polymer, but the dynamic property of a single dynamic covalent bond is limited, so that the synergistic orthogonal comprehensive property is difficult to form.

Therefore, in order to obtain dynamic polymers with diversity and synergistic orthogonal dynamics, a new dynamic covalent bond composition mode needs to be developed to solve the deficiencies existing in the existing dynamic polymers.

Disclosure of Invention

Against the above background, the present invention relates to a dynamic polymer comprising combined dynamic covalent bonds, characterized in that it comprises at least two classes of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is an organoboronate bond selected from, but not limited to, an organoboronate ring bond, an organoboronate monoester bond, an organoboronate silicon bond, and an organoboronate anhydride bond; the existence of the dynamic covalent bond as a polymerization linkage point and/or a crosslinking linkage point of the dynamic polymer is a necessary condition for forming or maintaining the structure of the dynamic polymer, and once the organic borate ester bond and the optional supermolecule hydrogen bond contained in the dynamic polymer are dissociated, the polymer system can be decomposed into any one or any of the following secondary units: monomers, polymer chain fragments, polymer clusters, and the like; meanwhile, the interconversion and dynamic reversibility can be realized between the dynamic polymer and the secondary unit through the bonding and dissociation of an organic boric acid ester bond and an optional supermolecule hydrogen bond. The dynamic polymer or composition has excellent dynamic reversibility, can show the functional characteristics of stimulus responsiveness, plasticity, self-repairing property, recoverability, reworkability and the like, and can obtain good energy absorption property and toughness.

The invention is realized by the following technical scheme:

the present invention relates to a dynamic polymer containing combined dynamic covalent bonds, characterized in that it contains at least two classes of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is an organoboronate bond selected from, but not limited to, an organoboronate ring bond, an organoboronate monoester bond, an organoboronate silicon bond, and an organoboronate anhydride bond; the presence of the dynamic covalent bond as a polymeric and/or cross-linking linkage point of the dynamic polymer is a necessary condition for forming or maintaining the dynamic polymer structure. The dynamic polymer and the composition thereof and the polymer chain topology structure in the raw material components are selected from linear, cyclic, branched, clustered, crosslinked and the combination thereof.

According to a preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a non-crosslinked structure containing at least two types of dynamic covalent bonds but no hydrogen bonds, and the sum of the degree of crosslinking of all types of dynamic covalent bonds is below the gel point. The structure is the simplest, and materials in the forms of solution, paste, glue and the like are also conveniently prepared.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a non-crosslinked structure comprising at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of all dynamic covalent bonds is below its gel point, the degree of crosslinking of supramolecular hydrogen bonds is below the gel point, and the sum of the degrees of crosslinking of dynamic covalent bonds and hydrogen bonds is below the gel point. The structure is simple, and the effect of synergetic orthogonality can be achieved by introducing the supermolecule hydrogen bond.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure containing at least two types of dynamic covalent bonds but no hydrogen bonds, wherein the degree of crosslinking of all types of dynamic covalent bonds is above the gel point. In this embodiment, the crosslinkability of the system can be ensured as long as one type of dynamic covalent bond remains above the gel point. The system has higher crosslinking degree and is favorable for obtaining materials with high mechanical properties.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure containing at least two types of dynamic covalent bonds but no hydrogen bonds, wherein the degree of crosslinking of the at least one type of dynamic covalent bonds is above the gel point and the degree of crosslinking of the at least one type of dynamic covalent bonds is below the gel point. The crosslinking degree is moderate, and the product performance can be conveniently regulated and controlled according to the requirement.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure containing at least two types of dynamic covalent bonds but no hydrogen bonds, wherein the degree of crosslinking of all types of dynamic covalent bonds is below the gel point, but the sum of the degrees of crosslinking is above the gel point. The crosslinking degree is low, and the product performance can be conveniently regulated and controlled according to the requirement.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or composition thereof; the dynamic polymer has a cross-linked structure and contains at least two types of dynamic covalent bonds and hydrogen bonds, wherein the cross-linking degree of all types of dynamic covalent bonds is above a gel point, and the cross-linking degree of the hydrogen bonds is above the gel point. In this embodiment, the crosslinkability of the system can be ensured as long as one type of dynamic covalent bond remains above the gel point. The crosslinking degree is extremely high, and a large number of hydrogen bonds are contained, so that the effects of high mechanical strength and synergetic orthogonality are conveniently obtained.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure comprising at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of all types of dynamic covalent bonds is above the gel point and the degree of crosslinking of hydrogen bonds is below the gel point. In this embodiment, the crosslinkability of the system can be ensured as long as one type of dynamic covalent bond remains above the gel point. The crosslinking degree is higher, the hydrogen bond content is lower, and the auxiliary supermolecule dynamic effect can be achieved.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure comprising at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of the at least one type of dynamic covalent bonds is above the gel point, the degree of crosslinking of the at least one type of dynamic covalent bonds is below the gel point, and the degree of crosslinking of the hydrogen bonds is above the gel point. The crosslinking degree is moderate, and meanwhile, hydrogen bonds are introduced, so that the effects of high elasticity, high mechanical strength and synergetic orthogonality are conveniently obtained.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure comprising at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of all types of dynamic covalent bonds is below the gel point and the degree of crosslinking of hydrogen bonds is above the gel point. The crosslinking degree is low, the product performance is conveniently regulated and controlled according to the needs, and the hydrogen bond with high content provides a synergistic orthogonal effect for the system.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure containing at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of all types of dynamic covalent bonds is below the gel point, the degree of crosslinking of hydrogen bonds is below the gel point, but the sum of the degrees of crosslinking of dynamic covalent bonds and hydrogen bonds is not lower than the gel point. The crosslinking degree is low, and the product performance can be conveniently regulated and controlled according to the requirement.

According to another preferred embodiment of the present invention, there is provided a dynamic polymer or a composition thereof, wherein the dynamic polymer has a crosslinked structure comprising at least two types of dynamic covalent bonds and hydrogen bonds, wherein the degree of crosslinking of the at least one type of dynamic covalent bonds is above the gel point, the degree of crosslinking of the at least one type of dynamic covalent bonds is below the gel point, and the degree of crosslinking of the hydrogen bonds is below the gel point. The crosslinking degree is low, the product performance can be conveniently regulated and controlled according to the requirement, and meanwhile, the supermolecule hydrogen bond provides auxiliary supermolecule dynamic action.

The invention is capable of other embodiments and of being practiced by those of ordinary skill in the art with the benefit of the teachings of the present invention.

The organoboronic acid cyclic ester bond described in the present invention may be selected from, but is not limited to, at least one of the following structures:

wherein one boron atom forms a cyclic organoborate unit with both oxygen atoms; the boron atom in the structure is required to be connected with one carbon atom through a boron-carbon bond, and at least one organic group is connected with the boron atom through the boron-carbon bond;represents a linkage to a hydrogen atom, a polymer chain, a cross-linking linkage, or any other suitable group/atom, the boron atom and at least one carbon atom being incorporated into the polymer chain through at least one of said linkages, respectively; different on the same carbon atomCan be linked to form a ring, +.>Or may be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; different +.>Can be linked to form a ring, +.>Or may be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; l is a linking group which can be incorporated into the polymer chain through an atom/group on L which can also be attached to +. >Connected into a ring.

The organoboronic acid monoester bond described in the present invention may be selected from, but is not limited to, at least one of the following structures:

wherein a single boron atom does not simultaneously form a six-membered ring or a cyclic organoborate unit of less than six-membered ring with two oxygen atoms bonded through atoms other than the boron atom; at least one carbon atom in the structure is connected with a boron atom through a boron-carbon bond;represents a linkage to a hydrogen atom, a polymer chain, a cross-linking linkage, or any other suitable group/atom, the boron atom and at least one carbon atom being incorporated into the polymer chain through at least one of said linkages, respectively; different +.>Can be connected into a ring without passing throughThe individual boron atoms being bound to different carbon atoms>Or may be linked to form a ring, +.>Or may be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; l (L) ₀ Is a linking group containing at least two backbone atoms, or may be bound by L ₀ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₀ The atoms/groups on the two sides C of the latter can also be +. >Connected into a ring; l (L) ₁ 、L ₂ 、L ₃ 、L ₄ As a linking group, also through L ₁ 、L ₂ 、L ₃ 、L ₄ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₁ 、L ₂ 、L ₃ 、L ₄ The atoms/groups may also be combined with the +.A.on both sides of the atom/group>Connected into a ring.

The organoboronate linkages described in the present invention may be selected from, but are not limited to, the following structures:

wherein at least one silicon borate bond (B-O-Si) is formed between the boron atom and the silicon atom; at least one carbon atom in the structure is linked to a boron atom by a boron carbon bond, and at least one organic group is linked to a boron atom by the boron carbon bond;represents a linkage to a polymer chain, a cross-linking linkage, or any other suitable group/atom through at least one of which the boron atom and the silicon atom, respectively, are attached to the polymer network.

The organic boric anhydride linkage described in the present invention may be selected from, but is not limited to, at least one of the following structures:

wherein at least one boron anhydride bond (B-O-B) is formed between the boron atom and the boron atom; each boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected with the boron atom through the boron-carbon bond;represents a linkage to a polymer chain, a cross-linking linkage, or any other suitable group/atom, at least two different boron atoms being respectively attached to the polymer network via at least one of said linkages; +. >Can be connected into a ring, wherein the ring can be selected from any of, but not limited to, aliphatic rings, aromatic rings, ether rings and condensed rings; l (L) ₃ 、L ₄ As a linking group, also through L ₃ 、L ₄ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₃ 、L ₄ The atoms/groups may also be combined with +.>Connected into a ring.

The organoboronic acid cyclic ester bond, organoboronic acid monoester bond, organoboronic acid silicon ester bond and organoboronic acid anhydride bond described in the present invention are formed by reacting an organoboronic acid motif with a dihydroxy motif, a monohydroxy motif, a silicon hydroxy/silicon hydroxy precursor, and an organoboronic acid motif, respectively.

The organoboronic acid moieties described in the present invention may be selected from, but are not limited to, organoboronic acid groups, organoboronic ester groups, organoborate groups, organoborohalogroups;

the dihydroxy moieties described in the present invention may be selected from, but are not limited to, 1, 2-diol moieties, 1, 3-diol moieties, ortho-diphenol hydroxy moieties, and 2-hydroxymethylphenol hydroxy moieties;

the monohydroxyl moiety described in the present invention may be selected from, but is not limited to, a mono-alkyl containing moiety, a mono-phenolic hydroxyl containing moiety, a poly-phenolic hydroxyl containing moiety in the meta position, a poly-phenolic hydroxyl containing moiety in the para position, and a poly-hydroxyl containing moiety separated by at least four atoms;

The silicon hydroxyl group in the present invention refers to a structural element (Si-OH) composed of a silicon atom and a hydroxyl group connected with the silicon atom, wherein the silicon hydroxyl group can be an organic silicon hydroxyl group (i.e. the silicon atom in the silicon hydroxyl group is connected with at least one carbon atom through a silicon carbon bond, and at least one organic group is connected with the silicon atom through the silicon carbon bond), or an inorganic silicon hydroxyl group (i.e. the silicon atom in the silicon hydroxyl group is not connected with the organic group), and is preferably an organic silicon hydroxyl group. In the invention, one hydroxyl (-OH) in the silicon hydroxyl is a functional group;

the silicon hydroxyl precursor refers to a structural element (Si-A) consisting of a silicon atom and a group which is connected with the silicon atom and can be hydrolyzed to obtain hydroxyl, wherein A is a group which can be hydrolyzed to obtain hydroxyl and can be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime and alkoxide. In the invention, one group (-A) of the silicon hydroxyl precursor which can be hydrolyzed to obtain hydroxyl is a functional group.

In embodiments of the invention, the optional supramolecular hydrogen bonding consists of hydrogen bonding between hydrogen bonding groups present at any one or more of the side groups, pendant groups, end groups, and dynamic polymer chain backbones (including side chains/branches/bifurcation chains). The hydrogen bond group preferably contains the following structural components:

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

wherein, the liquid crystal display device comprises a liquid crystal display device,representing a linkage to a polymer chain, a cross-linking linkage, or any other suitable group/atom (including hydrogen atoms).

In embodiments of the present invention, the dynamic polymer may be obtained by reacting as starting materials at least several of the following compounds:

an organoboron compound (I) containing an organoboric acid moiety; a compound (II) containing a dihydroxy moiety; a compound (III) containing a monohydroxyl moiety; a compound (IV) containing a silylhydroxy/silylhydroxy precursor; a compound (V) containing at least one of various hydroxyl groups and an organoboric acid group; compound (VI) containing said dynamic covalent bond and other reactive groups; a compound (VII) which does not contain an organoboronic acid moiety, various hydroxyl moieties, and a dynamic covalent bond but contains other reactive groups.

The compounds (I) - (VII) can be small molecular compounds with molecular weight not more than 1000Da or large molecular compounds with molecular weight more than 1000 Da; the organoboron compound (I), compound (II), compound (III), compound (IV) and compound (V) may or may not contain other reactive groups.

The present invention provides a method for preparing a dynamic polymer containing a combination of dynamic covalent bonds, said dynamic polymer containing a linear or cyclic structure, preferably prepared by at least one of the following means (but the invention is not limited thereto):

first, it is obtained by the reaction of at least the following components in the reaction to form a dynamic covalent bond: at least one organoboron compound (I), at least two hydroxyl group-containing compounds (selected from the group consisting of organoboron group-containing compounds (I), compounds (II) to compounds (IV), and the like); wherein the organoboron compound (I) and the hydroxyl-containing compound each contain at most two functional groups;

second, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one organoboron compound (I), at least two hydroxyl-containing compounds; or a combination of at least one organoboron compound (I), at least two hydroxyl-containing compounds and at least one compound (VII); wherein both the organoboron compound (I) and the hydroxyl-containing compound contain one functional group and one other reactive group, and the compound (VII) contains at most two other reactive groups;

third, by the reaction of at least the following components to form a dynamic covalent bond: at least one compound (V), or with at least one organoboron compound (I) or at least two hydroxyl-containing compounds or at least one organoboron compound (I) and at least two hydroxyl-containing compounds; wherein the compound (V), the organoboron compound (I) and the hydroxyl-containing compound each contain at most two functional groups.

Fourth, obtained by the reaction of at least the following components to form a common covalent bond: at least one compound (VI), or with at least one compound (VII); wherein, at least two types of dynamic covalent bonds are contained in the compound (VI), and the compound (VI) and the compound (VII) both contain at most two other reactive groups.

The present invention provides a method for preparing a dynamic polymer based on combined dynamic covalent bonds, the dynamic polymer having a branched structure, which is preferably prepared by at least one of the following ways (but the invention is not limited thereto):

first, it is obtained by the reaction of at least the following components in the reaction to form a dynamic covalent bond: at least one organoboron compound (I), at least two hydroxyl-containing compounds; wherein at least one of the organoboron compound (I), the hydroxyl-containing compound contains at least three functional groups, and the combination thereof does not result in ordinary covalent crosslinking above the gel point;

second, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one organoboron compound (I), at least two hydroxyl-containing compounds; wherein at least one compound of the organoboron compound (I) and the hydroxyl-containing compound contains at least one functional group and at least one other reactive group and the sum of the number of functional groups and other reactive groups is not less than three, and the combination thereof does not produce ordinary covalent crosslinking above the gel point;

Third, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one compound (V), at least one compound (VII), or both, with at least one organoboron compound (I) or at least two hydroxyl-containing compounds or at least one organoboron compound (I) and at least two hydroxyl-containing compounds; wherein the compound (V), the organoboron compound (I), the hydroxyl-containing compound each contain up to two functional groups and at least one of the compound (V) or the organoboron compound (I) or the hydroxyl-containing compound contains at least one other reactive group, and combinations thereof do not result in ordinary covalent crosslinking above the gel point.

Fourth, obtained by the reaction of at least the following components to form a common covalent bond: at least one compound (VI), or with at least one compound (VII); wherein at least two types of dynamic covalent bonds are contained in the compound (VI), at least one compound (VI) or at least one compound (VII) contains at least three other reactive groups, and the combination thereof does not result in a common covalent cross-link above the gel point.

The present invention provides a method for preparing a dynamic polymer based on a combined dynamic covalent bond, wherein the dynamic polymer has a dynamic cross-linked structure, and is preferably prepared by at least one of the following modes (but the invention is not limited thereto):

First, it is obtained by the reaction of at least the following components in the reaction to form a dynamic covalent bond: at least one organoboron compound (I), at least two hydroxyl-containing compounds; wherein the organoboron compound (I) and the hydroxyl-containing compound contain at least two functional groups and at least one organoboron compound (I) or at least one hydroxyl-containing compound contains at least three functional groups and the combination thereof does not result in ordinary covalent crosslinking above the gel point;

second, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one organoboron compound (I), at least two hydroxyl-containing compounds; wherein the sum of the numbers of functional groups and other reactive groups contained in the organoboron compound (I) and the hydroxyl-containing compound is not less than two, and the sum of the numbers of functional groups and other reactive groups contained in the at least one organoboron compound (I) or the at least one hydroxyl-containing compound is not less than three, and the combination thereof does not produce ordinary covalent crosslinking above the gel point;

third, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one compound (V), or with at least one compound (VII) or at least one organoboron compound (I) or at least two hydroxyl-containing compounds or at least one organoboron compound (I) and at least two hydroxyl-containing compounds; wherein the compound (v), the organoboron compound (I), the hydroxyl-containing compound each contain at least two functional groups and at least one of the compound (v) or the organoboron compound (I) or the hydroxyl-containing compound contains at least three functional groups, or at least one of the compound (v) or the organoboron compound (I) or the hydroxyl-containing compound contains at least one other reactive group and the combination thereof does not result in a common covalent cross-linking above the gel point;

Fourth, obtained by the reaction of at least the following components to form a common covalent bond: at least one compound (VI), or with at least one compound (VII); wherein, at least two types of dynamic covalent bonds are contained in the compound (VI), the compound (VI) and the compound (VII) both contain at least two other reactive groups, at least one compound (VI) or at least one compound (VII) contains at least three other reactive groups, and the combination of the compounds does not generate common covalent cross-linking above a gel point.

In the present invention, the preparation process of the dynamic polymer by using the above embodiments has simple steps, easy operation and strong controllability, and thus is a preferred embodiment of the present invention.

The invention also provides an energy absorption method, which is characterized in that a dynamic polymer containing combined dynamic covalent bonds is provided, and is used as an energy absorption material for absorbing energy, and the energy absorption method comprises at least two types of dynamic covalent bonds and optional hydrogen bonds; wherein the dynamic covalent bond is an organoboronate bond selected from, but not limited to, an organoboronate ring bond, an organoboronate monoester bond, an organoboronate silicon bond, and an organoboronate anhydride bond; the existence of the dynamic covalent bond as a polymerization linkage point and/or a crosslinking linkage point of the dynamic polymer is a necessary condition for forming or maintaining the structure of the dynamic polymer, and once the organic borate ester bond and the optional supermolecule hydrogen bond contained in the dynamic polymer are dissociated, the polymer system can be decomposed into any one or any of the following secondary units: monomers, polymer chain fragments, polymer clusters, and the like; meanwhile, the interconversion and dynamic reversibility can be realized between the dynamic polymer and the secondary unit through the bonding and dissociation of an organic boric acid ester bond and an optional supermolecule hydrogen bond.

In embodiments of the present invention, the dynamic polymer morphology containing combined dynamic covalent bonds may be solutions, emulsions, pastes, gums, common solids, elastomers, gels (including hydrogels, organogels, oligomer-swollen gels, plasticizer-swollen gels, ionic liquid-swollen gels), foams, and the like.

In the embodiment of the invention, certain other polymers, auxiliary agents and fillers which can be added can be optionally added in the preparation process of the dynamic polymer for blending to jointly form the dynamic polymer.

In the embodiment of the invention, the dynamic polymer or the composition performance thereof is adjustable in a large range, and has wide application prospect in the fields of military aerospace equipment, functional coatings, biological medicine, biomedical materials, energy sources, buildings, bionics, intelligent materials and the like. In particular, the material can be applied to manufacturing shock absorbers, energy absorbing materials, buffer materials, impact resistant protective materials, sports protective products, police protective products, force sensors, self-repairing coatings, self-repairing plates, self-repairing adhesives, bulletproof glass interlayer adhesives, tough materials, sound insulation and noise elimination materials, shape memory materials, sealing elements, toys and other products.

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

(1) The dynamic polymer at least contains two types of dynamic covalent organic borate bonds, and the strength, the structure, the dynamic property, the responsiveness, the formation conditions and the like of the dynamic covalent organic borate bonds of different types are different, so that the synergistic and orthogonal performance effects can be achieved; moreover, the organic boric acid ester bonds can be mutually exchanged and converted under certain conditions, so that the structure and the performance of the material are more adjustable.

(2) The dynamic polymers of the present invention may optionally also contain hydrogen bonds. On the basis of containing at least two types of organic borate bonds, the strength, the dynamic property, the responsiveness and other properties which can be adjusted in a large range can be obtained by adding hydrogen bonding; meanwhile, the number of the introduced hydrogen bonds and the linking structure of the hydrogen bonds and the polymer chain can be conveniently regulated, so that the dynamic polymer with controllable hydrogen bonds and controllable glass transition temperature is obtained. The dynamic covalent organic borate bond and the hydrogen bond can be broken in a sacrificial bond mode under the action of external force, so that a large amount of energy can be dissipated, and the cross-linked polymer can be provided with excellent tensile toughness and tear resistance in a specific structure; on the other hand, super-stretch stretching rate can be obtained; because the strength of the dynamic covalent organic borate bond is generally higher than that of the hydrogen bond, when the dynamic covalent organic borate bond is damaged by external force, the hydrogen bond and the organic borate bond can change sequentially, and the hydrogen bond is generally dissociated first, so that the gradual dissipation of force is generated, and the material tolerance to the external force is improved. In addition, self-repairing, plasticity and reworkability of orthogonality can be obtained based on the dynamics of organoborate bonds and hydrogen bonds.

(3) The dynamic reactivity of the organic boric acid ester bond in the dynamic polymer is strong, and the dynamic reaction condition is mild. Compared with other existing dynamic covalent systems, the invention fully utilizes the good thermal stability and high dynamic reversibility of the organic borate bond, can realize the synthesis and dynamic reversibility of the dynamic polymer under the conditions of no need of catalyst, high temperature, illumination or specific pH, improves the preparation efficiency, reduces the limitation of the use environment and expands the application range of the polymer. In addition, by selectively controlling other conditions (e.g., adding adjuvants, adjusting reaction temperature, etc.), the dynamic covalent chemical equilibrium can be accelerated or quenched in a desired state under appropriate circumstances, which is more difficult to achieve in existing supramolecular chemistry as well as dynamic covalent systems.

(4) In the invention, the dynamic reversibility of organic borate ester bonds and optional supermolecule hydrogen bonds in the dynamic polymer is utilized, so that the polymer can show thickening responsiveness when being impacted by external force, and can achieve multiple absorption and dissipation of impact energy through reversible rupture of the organic borate ester bonds and the hydrogen bonds. For a non-crosslinked system, the thickening response produces complete viscosity loss enhancement, and strong energy absorption is achieved; for dynamic crosslinking systems, however, a viscous-elastic transition can be produced, while at the same time the viscous losses can be reduced.

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

Detailed Description

The present invention relates to a dynamic polymer containing combined dynamic covalent bonds, characterized in that it contains at least two classes of dynamic covalent bonds and optionally hydrogen bonds; wherein the dynamic covalent bond is an organoboronate bond selected from, but not limited to, an organoboronate ring bond, an organoboronate monoester bond, an organoboronate silicon bond, and an organoboronate anhydride bond; the existence of the dynamic covalent bond as a polymerization linkage point and/or a crosslinking linkage point of the dynamic polymer is a necessary condition for forming or maintaining the structure of the dynamic polymer, and once the organic borate ester bond and the optional supermolecule hydrogen bond contained in the dynamic polymer are dissociated, the polymer system can be decomposed into any one or any of the following secondary units: monomers, polymer chain fragments, polymer clusters, and the like; meanwhile, the interconversion and dynamic reversibility can be realized between the dynamic polymer and the secondary unit through the bonding and dissociation of an organic boric acid ester bond and an optional supermolecule hydrogen bond. The dynamic polymer or composition has excellent dynamic reversibility, can show the functional characteristics of stimulus responsiveness, plasticity, self-repairing property, recoverability, reworkability and the like, and can obtain good energy absorption property and toughness.

The term "polymerization" reaction/action, as used herein, is a chain growth process/action and refers to a process in which lower molecular weight reactants synthesize a product having a higher molecular weight by polycondensation, polyaddition, ring opening polymerization, etc. reaction forms. The reactant is generally a compound such as a monomer, an oligomer, or a prepolymer having a polymerization ability (i.e., capable of spontaneously polymerizing or capable of polymerizing by an initiator or external energy). The product obtained by polymerizing 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 noted that "polymerization" as used herein includes a linear growth process of the reactant molecular chains, a branching process of the reactant molecular chains, a cyclization process of the reactant molecular chains, and a crosslinking process of the reactant molecular chains. In embodiments of the invention, "polymerization" also includes chain growth caused by supermolecular hydrogen bonding.

The term "crosslinking" reaction/action as used herein refers to the process of chemical and/or supramolecular chemical attachment of reactant molecules to form a product having two-dimensional, three-dimensional clusters and thus three-dimensional infinite networks by dynamic covalent bonds and/or supramolecular hydrogen bonds between reactant molecules and/or within reactant molecules. In the crosslinking process, the polymer chains generally grow continuously in two-dimensional/three-dimensional directions, gradually form clusters (which can be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Unless otherwise specified, the crosslinked structure in the present invention includes only a three-dimensional infinite network (structure) above (including, and below) the gel point, and the uncrosslinked structure refers to a linear, cyclic, branched, etc. structure below the gel point and a two-dimensional, three-dimensional cluster structure.

The term "gel point" as used herein means the point of reaction at which the reactant, during crosslinking, undergoes a sudden increase in viscosity and begins to gel, initially reaching a three-dimensional infinite network, also known as the percolation threshold. The cross-linked reaction product above the gel point has a three-dimensional infinite network structure, the cross-linked network forms a whole and spans the whole polymer structure, and the cross-linked structure is stable and firm; the cross-linked reaction product below the gel point, which is only a loosely linked structure, does not form a three-dimensional infinite network structure, only exists in a small amount of two-dimensional or three-dimensional network structure locally, and does not belong to a cross-linked network capable of forming one whole across the entire polymer structure.

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

The dynamic polymer has a polymer chain topological structure selected from linear, cyclic, branched, clustered, crosslinked and a combination thereof; the composition and chain topology of the polymer in the starting materials may also be selected from the group consisting of linear, cyclic, branched, clustered, crosslinked and combinations thereof.

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

Wherein, the 'cyclic' structure refers to that the polymer molecular chain exists in the form of a cyclic chain, and the polymer molecular chain comprises a cyclic structure in the forms of single rings, multiple rings, bridged rings, embedded rings and the like; for the cyclic structure, it may be formed by intramolecular and/or intermolecular ring formation of a linear or branched polymer, or may be prepared by a method such as ring-expanding polymerization.

Wherein, the branched structure refers to a structure containing side chains, branched chains, bifurcation chains and the like on a polymer molecular chain, including but not limited to star-shaped, H-shaped, comb-shaped, branch-shaped, hyperbranched and the combination thereof, and further combination thereof with linear and cyclic structures, such as a linear chain end connection cyclic structure, a cyclic structure is combined with the comb-shaped structure, a branch-shaped chain end connection cyclic chain and the like; for the side chains, branches and bifurcation chains of the polymer, it may have a multi-stage structure, for example, one or more stages of branches may be continued on the branches of the polymer molecule chain. As for the "branched structure", various methods for its preparation are generally known to those skilled in the art and can be formed, for example, by polycondensation of monomers containing long-chain side groups, or by chain transfer reactions of free radicals during the polyaddition, or by extension of branched structures on the linear molecular chain by irradiation and chemical reactions. Further intramolecular and/or intermolecular reactions (crosslinking) of the branched structure may result in clusters and crosslinked structures.

Wherein, the said "cluster" structure refers to the two-dimensional/three-dimensional structure below the gel point generated by the intramolecular and/or intermolecular reaction of the polymer chain.

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

In the embodiments of the present invention, the dynamic polymer, its composition and the raw material composition may have only one kind of polymer with a topological form, or may be a mixture of polymers with various topological forms.

The dynamic polymers may contain dynamic covalent bonds at any suitable position of the polymer. For non-crosslinked dynamic polymers, dynamic covalent bonds may be contained on any of the polymer chain backbones; for crosslinked dynamic polymers, dynamic covalent bonds may be contained on any of the polymer chain backbones; the present invention also does not exclude the inclusion of dynamic covalent bonds on the side groups and/or end groups of the polymer chains; among them, the polymer chain skeleton preferably contains a dynamic covalent bond. The dynamic covalent bond can be reversibly broken and regenerated under normal conditions; under suitable conditions, dynamic covalent bonds at any position in the dynamic polymer may participate in dynamic reversible exchange.

In the present invention, the polymer chain skeleton refers to a skeleton of any segment existing in a polymer network structure, and includes a crosslinked network chain in a crosslinked structure and its side chains, branched chains, and a polymer chain skeleton in a non-crosslinked structure and its side chains, branched chains, and branched chains.

In the present invention, the term "side chain" refers to a chain structure having a molecular weight exceeding 1000Da, which is linked to the backbone of a polymer chain in the polymer structure and is distributed beside the backbone; wherein, the branched chain and the forked chain refer to a chain structure which is forked from a polymer chain framework or any other chain and has the molecular weight of more than 1000 Da; for simplicity, the side chains, branches, and bifurcation chains are collectively referred to as side chains unless otherwise specified, when the molecular weight exceeds 1000 Da. 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 side chains and side groups, they may have a multi-stage structure, i.e., the side chain may continue to bear side groups and side chains, and the side chain of the side chain may continue to bear side groups and side chains, which also include chain structures such as branched and bifurcated chains. Wherein, the end group refers to a chemical group which is connected with the polymer chain framework and is positioned at the tail end of the chain framework in the polymer structure; in the present invention, the side groups may have terminal groups in particular cases.

In the present invention, the dynamic polymer contains at least two types of dynamic covalent bonds, that is, at least two types selected from, but not limited to, organoboronate cyclic ester bonds, organoboronate monoester bonds, organoboronate silicon ester bonds and organoboronate anhydride bonds, and thus contains a combined dynamic covalent bond structure; at the same time, it may also contain optional hydrogen bonds. The dynamic polymer or the composition thereof can be regulated and controlled in terms of chemical structure, topological structure, composition components, morphology and the like, so that ideal performance is obtained.

In the present invention, the at least two types of dynamic covalent bonds may be on the same polymer or on different polymers; the dynamic covalent bond and the optional hydrogen bond groups may be on the same polymer or on different polymers. When different dynamic covalent bonds or dynamic covalent bonds and hydrogen bond groups are on different polymers, the dynamic polymer is a polymer composition; hydrogen bonding groups may also be present in small molecules and fillers, among others.

In the present invention, when multiple polymeric ingredients are present, the ingredients may be compatible or incompatible; when at least one crosslinked component is present, the different components may be mutually dispersed, interpenetrating or partially interpenetrating, but the present invention is not limited thereto.

In embodiments of the invention, the optional supramolecular hydrogen bonding may be comprised of hydrogen bonding between hydrogen bonding groups present at any one or more of the side chain/branched chain, pendant group, end group, and polymer chain backbone (including side chain/branched chain) present in the dynamic polymer and its composition. The hydrogen bond groups may also be present in other components of the dynamic polymer composition, including but not limited to small molecules, polymers, fillers, either simultaneously or alone.

In the invention, when the dynamic properties of the dynamic covalent bond and the supermolecule hydrogen bond are strong enough, if the respective crosslinking degree and the sum thereof are below the gel point, the viscosity is easy to be increased and the viscosity loss is increased when the dilatant characteristic occurs; if one of them has a crosslinking degree of at least the gel point or the sum of the crosslinking degrees is at least the gel point, the viscous-elastic transition is liable to occur when the dilatant characteristic occurs. Thus, crosslinking and non-crosslinking are distinctive and can be reasonably designed and implemented by those skilled in the art based on the application and requirements. The organoboronic acid cyclic ester bond described in the present invention may be selected from at least one of the following structures:

wherein one boron atom forms a cyclic organoborate unit with both oxygen atoms; the boron atom in the structure is required to be connected with one carbon atom through a boron-carbon bond, and at least one organic group is connected with the boron atom through the boron-carbon bond;represents a linkage to a hydrogen atom, a polymer chain, a cross-linking linkage, or any other suitable group/atom, the boron atom and at least one carbon atom being incorporated into the polymer chain through at least one of said linkages, respectively; different on the same carbon atom Can be linked to form a ring, +.>Or may be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; different +.>Can be linked to form a ring, +.>Or may be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; wherein L is a linking group, which may include carbon atoms and heteroatoms such as oxygen, nitrogen, sulfur, etc., the nearest backbone atom linking the two hydroxyl groups being no more than 3 and not forming a resorcinol; the atoms/groups on L can also be combined with +.>Connected into a ring.

In the present invention, the organoboronic acid cyclic ester bond is preferably formed by reacting an organoboronic acid moiety with a dihydroxy moiety. The dihydroxy moiety may be selected from, but is not limited to, a 1, 2-diol moiety, a 1, 3-diol moiety, an ortho-diphenol moiety, a 2-hydroxymethylphenol hydroxy moiety;

wherein the 1, 2-diol moiety may be selected from ethylene glycol moleculesA residue formed after the loss of at least one non-hydroxylic hydrogen atom;

Wherein the 1, 3-diol moiety may be selected from 1, 3-propanediol moleculesA residue formed after the loss of at least one non-hydroxylic hydrogen atom;

wherein the ortho-diphenol hydroxyl moiety may be selected from the group consisting of a residue formed after ortho-diphenol loses a non-hydroxyl hydrogen atom on at least one aromatic ring, a residue formed after hetero-ortho-diphenol loses a non-hydroxyl atom on at least one aromatic ring;

wherein the 2-hydroxymethylphenol hydroxy moiety is selected from the group consisting of 2-hydroxymethylphenol, and 2-hydroxymethylphenol residues formed after the loss of at least one non-hydroxylic hydrogen atom.

In the present invention, the organoboronic acid monoester bond may be selected from at least one of the following structures:

wherein a single boron atom does not simultaneously form a six-membered ring or a cyclic organoborate unit of less than six-membered ring with two oxygen atoms bonded through atoms other than the boron atom; at least one carbon atom in the structure is connected with a boron atom through a boron-carbon bond;represents a linkage to a hydrogen atom, a polymer chain, a cross-linking linkage, or any other suitable group/atom, the boron atom and at least one carbon atom being incorporated into the polymer chain through at least one of said linkages, respectively; different +. >Can be linked to form a ring, not on the different carbon atoms linked by said single boron atom>Or may be linked to form a ring, +.>Can also be connected intoA ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; l (L) ₀ Is a linking group containing at least two backbone atoms, or may be bound by L ₀ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₀ The atoms/groups on the two sides C of the latter can also be +.>Connected into a ring; l (L) ₁ 、L ₂ 、L ₃ 、L ₄ As a linking group, also through L ₁ 、L ₂ 、L ₃ 、L ₄ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₁ 、L ₂ 、L ₃ 、L ₄ The atoms/groups may also be combined with the +.A.on both sides of the atom/group>Connected into a ring.

The organoboronic acid monoester linkages described in the present invention are preferably formed by reacting an organoboronic acid moiety with a monohydrocarbonyl moiety, which can be selected from, but is not limited to, a monoalkol hydroxy moiety, a monophenol hydroxy moiety, a polyphenol hydroxy group in the meta position, a polyphenol hydroxy group in the para position, and a hydroxy group in a polyhydroxy compound spaced by at least four atoms;

wherein the mono-alkyl hydroxyl moiety, which refers to an alkane group carbon atom to which the hydroxyl group is directly attached, includes heteroatom-attached alkanes; the monoalkinol hydroxyl radical, which refers to an alkene in which the carbon atom directly attached to the hydroxyl group is an unsaturated alkene carbon atom, including heteroatom-attached alkenes; the monophenol hydroxy group unit refers to that the carbon atom directly connected with the hydroxy group is an aromatic hydrocarbon carbon atom and comprises heteroaromatic hydrocarbon; if two or more monohydroxyl moieties are present in the compound, at least the polyphenol hydroxyl groups in the meta-position, the polyphenol hydroxyl groups in the para-position, and the hydroxyl groups in the polyhydroxy compound spaced by at least four atoms are possible.

The organoboronate silicon ester bond described in the present invention has the structure shown below:

The silicon hydroxyl group refers to a structural element (Si-OH) formed by a silicon atom and a hydroxyl group connected with the silicon atom, wherein the silicon hydroxyl group can be an organic silicon hydroxyl group (namely, the silicon atom in the silicon hydroxyl group is connected with at least one carbon atom through a silicon carbon bond, and at least one organic group is connected with the silicon atom through the silicon carbon bond), or can be an inorganic silicon hydroxyl group (namely, the silicon atom in the silicon hydroxyl group is not connected with the organic group), and is preferably an organic silicon hydroxyl group. In the present invention, one hydroxyl (-OH) group in the silicon hydroxyl group is a functional group.

Wherein the silicon hydroxyl precursor refers to a structural element (Si-A) composed of a silicon atom and a group which is connected with the silicon atom and can be hydrolyzed to obtain hydroxyl, wherein A is a group which can be hydrolyzed to obtain hydroxyl and can be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime and alkoxide. In the invention, one group (-A) of the silicon hydroxyl precursor which can be hydrolyzed to obtain hydroxyl is a functional group.

The organoboronic anhydride linkages described in the present invention, which may be formed by the reaction of suitable organoboronic acid moieties, may be selected from at least one of the following structures:

wherein at least one boron anhydride bond (B-O-B) is formed between the boron atom and the boron atom; each boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected with the boron atom through the boron-carbon bond;represents a linkage to a polymer chain, a cross-linking linkage, or any other suitable group/atom, at least two different boron atoms being respectively attached to the polymer network via at least one of said linkages; +.>May be linked to form a ring, which may be selected from, but is not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, any combination of the above; l (L) ₃ 、L ₄ As a linking group, also through L ₃ 、L ₄ The atoms/groups on the polymer chain being incorporated into the polymer chain, L ₃ 、L ₄ The atoms/groups may also be combined with +.>Connected into a ring.

The organoboronic acid moiety described in the present invention may be selected from, but is not limited to, at least one of an organoboronic acid group, an organoboronic ester group, an organoborate group, an organoborohalogenoalkyl group.

In an embodiment of the present invention, the organic boric acid group refers to a structural element (B-OH) composed of a boron atom and at least one hydroxyl group attached to the boron atom, wherein the boron atom is attached to at least one carbon atom through a boron carbon bond, and at least one organic group is attached to the boron atom through the boron carbon bond.

In an embodiment of the present invention, the organic borate group refers to a structural element (B-OR in which R is a hydrocarbon group mainly comprising carbon and hydrogen atoms OR a silane group mainly comprising silicon and hydrogen atoms and bonded to oxygen atoms through carbon atoms OR silicon atoms) composed of a boron atom, at least one oxygen atom bonded to the boron atom, and a hydrocarbon group OR silane group bonded to the oxygen atom, and in which at least one organic group is bonded to the boron atom through a boron carbon bond.

In an embodiment of the present invention, the organic borate group means that the compound structure at least comprises one structural element (B-O) consisting of a boron atom and at least one oxyanion attached to the boron atom ^- ) And at least one positive ion (M ⁿ⁺ ) And wherein the boron atom is attached to at least one carbon atom by a boron carbon bond and wherein at least one organic group is attached to the boron atom by the boron carbon bond.

In an embodiment of the present invention, the organoboron haloalkyl group refers to a structural element (B-F, B-Cl, B-Br, B-I) consisting of a boron atom and at least one halogen atom (F, cl, br, I) attached to the boron atom, wherein the boron atom is attached to at least one carbon atom via a boron carbon bond and at least one organic group is attached to the boron atom via the boron carbon bond.

The optional supermolecule hydrogen bonding in the present invention is any suitable supermolecule bonding established by hydrogen bonding, and generally hydrogen bonding in the form of Z-H … Y is generated by covalent bonding of a hydrogen atom covalently linked to an atom Z with high electronegativity and an atom Y with high electronegativity and a small radius, and hydrogen is used as a medium between Z and Y, wherein Z, Y is any suitable atom with high electronegativity and a small radius, which may be the same element or different element, and may be selected from F, N, O, C, S, cl, P, br, I and other atoms, more preferably F, N, O atoms, and still more preferably O, N atoms. Wherein the supermolecular hydrogen bonding may exist as supermolecular polymerization and/or crosslinking and/or intra-chain cyclization, i.e., the hydrogen bonding may only serve to connect two or more segment units to increase the polymer chain size but not to crosslink the supermolecule, or the hydrogen bonding may only serve to crosslink the interchain supermolecule, or to ring only within the chain, or a combination of any two or more of the three. The present invention also does not exclude hydrogen bonding to effect grafting.

In embodiments of the present invention, the hydrogen bond may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by the donor (H, i.e., a hydrogen atom) and the acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of the hydrogen bond group, and each H … Y is combined into one tooth. In the following figures, the hydrogen bonding conditions of the mono-, di-and tridentate hydrogen bonding groups are schematically illustrated:

the bonding conditions of the hydrogen bonds of the first tooth, the second tooth and the third tooth can be specifically exemplified as follows:

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 effects of promoting the dynamic polymer to keep a balance structure and improving the mechanical properties (modulus and strength) can be achieved. If the number of teeth of the hydrogen bond is small, the strength is low, the dynamics of the hydrogen bond action is strong, and the dynamic performance can be provided together with the dynamic covalent organic borate bond. In embodiments of the invention, hydrogen bonding of no more than four teeth is preferred.

In embodiments of the invention, the supramolecular hydrogen bonding may be produced by non-covalent interactions that exist between any suitable hydrogen bonding groups. Wherein the hydrogen bond group may contain only a hydrogen bond donor, or only a hydrogen bond acceptor, or both a hydrogen bond donor and an acceptor, preferably both a hydrogen bond donor and an acceptor. Wherein, the hydrogen bond group preferably contains the following structural components:

wherein, the liquid crystal display device comprises a liquid crystal display device,representing a linkage to a polymer chain, a cross-linking linkage, or any other suitable group/atom (including hydrogen atoms). In the embodiment of the present invention, the hydrogen bond group is preferably selected from an amide group, a carbamate group, a urea group, a thiocarbamate group, derivatives of the above, and the like.

In the present invention, the hydrogen bond group may be present only on the polymer chain skeleton (including side chains/branched/forked chains), referred to as skeleton hydrogen bond group; or may be present only on polymer chain pendant groups (also including pendant multi-level structures), referred to as pendant hydrogen bonding groups; or may be present only on polymer chain/small molecule end groups, called end hydrogen bonding groups; may also be present at least two of the polymer chain backbone, polymer chain side groups, polymer chain/small molecule end groups. When present simultaneously on at least two of the polymer chain backbone, polymer chain side groups, polymer chain/small molecule end groups, hydrogen bonds may be formed between hydrogen bond groups at different positions in certain circumstances, for example, the backbone hydrogen bond groups may form hydrogen bonds with the side hydrogen bond groups.

Examples of suitable backbone hydrogen bonding groups include, but are not limited to:

among these, suitable pendant hydrogen bond groups/terminal hydrogen bond groups may have, in addition to the skeletal hydrogen bond group structure described above, more specific examples are (but the invention is not limited thereto):

/>

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

In the present invention, one or more hydrogen bond groups may be contained in the same dynamic polymer. The hydrogen bonding groups may be formed by any suitable chemical reaction, for example: formed by covalent reactions between carboxyl groups, acyl halide groups, anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reactions between succinimidyl ester groups and amino, hydroxyl, sulfhydryl groups.

In the present invention, the supramolecular hydrogen bonding may be generated during dynamic covalent crosslinking of the dynamic polymer; or the dynamic covalent crosslinking is carried out after the supermolecule hydrogen bond is generated in advance; the supermolecule hydrogen bonding can also be generated in the subsequent forming process of the dynamic polymer after the dynamic covalent crosslinking is formed, but the invention is not limited to the method.

In the invention, because the strength and the dynamic property of the organic borate bond of different types are different, the performances of different hydrogen bond structures are also different, and the strength, the dynamic property, the responsiveness and other performances which are adjustable in a large range can be obtained on the basis of containing at least two types of organic borate bonds and by adding the hydrogen bond action; meanwhile, the number of the introduced hydrogen bonds and the linking structure of the hydrogen bonds and the polymer chain can be conveniently regulated, so that the dynamic polymer with controllable hydrogen bonds and controllable glass transition temperature is obtained. The dynamic covalent organic borate bond and the hydrogen bond can be broken in a sacrificial bond mode under the action of external force, so that a large amount of energy can be dissipated, and the cross-linked polymer can be provided with excellent tensile toughness and tear resistance in a specific structure; on the other hand, super-stretch stretching rate can be obtained; because the strength of the dynamic covalent organic borate bond is generally higher than that of the hydrogen bond, when the dynamic covalent organic borate bond is damaged by external force, the hydrogen bond and the organic borate bond can change sequentially, and the hydrogen bond is generally dissociated first, so that the gradual dissipation of force is generated, and the material tolerance to the external force is improved. In addition, the dynamic polymer of the invention can also obtain self-repairing property, plasticity and reworkability of orthogonality based on the dynamic property of organic borate ester bonds and hydrogen bonds.

an organoboron compound (I) containing an organoboric acid moiety; a compound (II) containing a dihydroxy moiety; a compound (III) containing a monohydroxyl moiety; a compound (IV) containing a silylhydroxy/silylhydroxy precursor; a compound (V) containing at least one of various hydroxyl groups and an organoboronic acid group; compound (VI) containing said dynamic covalent bond and other reactive groups; a compound (VII) which does not contain an organoboronic acid moiety, various hydroxyl moieties, and a dynamic covalent bond but contains other reactive groups.

The other reactive groups refer to groups capable of spontaneously or undergoing chemical reaction under the conditions of an initiator or light, heat, irradiation, catalysis, etc. to form common covalent bonds, and suitable groups include, but are not limited to: carboxyl, carbonyl, acyl, amido, acyloxy, amino, aldehyde, sulfonic, sulfonyl, mercapto, alkenyl, alkynyl, cyano, oxazinyl, oxime, hydrazino, guanidino, halogen, isocyanate, anhydride, epoxy, acrylate, acrylamide, maleimide, succinimidyl ester, norbornene, azo, azido, heterocyclic, triazolinedione, carbon radical, oxygen radical, and the like; amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, and acrylamide groups are preferred.

The other reactive groups in the invention play a role in the system, firstly, derivatization reaction is carried out to prepare hydrogen bond groups, and secondly, common covalent bonds are formed between the compounds or between the compounds and other compounds or between the compounds and reaction products of the compounds and other compounds directly through the reaction of the other reactive groups, so that the molecular weight of the compounds and/or the reaction products of the compounds and the reaction products of the compounds are increased/the functionalities are increased.

In an embodiment of the present invention, the organoboron group described in the organoboron compound (I) containing an organoboron moiety may be selected from, but is not limited to, any one or any of the following structures:

wherein K is ₁ Is a group directly attached to the boron atomAn atom selected from any one of the following structures: hydrogen atoms, heteroatom groups, aliphatic hydrocarbyloxy groups, aromatic hydrocarbyloxy groups, small molecule hydrocarbyl groups of molecular weight no more than 1000Da, polymer chain residues of molecular weight greater than 1000 Da; when K is ₁ When the compound is aliphatic alkoxy or aromatic alkoxy, the organoboron compound (I) contains an organoboric acid group and an organoboric acid ester group, which is helpful for regulating and controlling the parameters such as solubility, reaction rate, reaction degree and the like of the compound, and can be used for regulating and controlling the performances such as dynamic property and the like of the dynamic polymer. Wherein the cyclic structure in B4 is a non-aromatic or aromatic boron heterocyclic group containing at least one organic boric acid group, and boron atoms are arranged in the cyclic structure, and the cyclic structure can be a small molecular ring or a large molecular ring, and is preferably a 3-100-membered ring, more preferably a 3-50-membered ring, and even more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic structure in B4 are each independently a carbon atom, a boron atom or other heteroatom, and at least one ring-forming atom is a boron atom and constitutes an organoboronic acid group, and at least one ring-forming atom is attached to the other atoms of the compound; the hydrogen atoms on the ring atoms of the cyclic structures in B4 can be substituted or unsubstituted; the annular structure in the B4 can be a single-ring structure, a multi-ring structure, a spiro structure, a condensed ring structure, a bridge ring structure or a nested ring structure; Represents a linkage to other atoms of the compound; the boron atoms in the various structures are attached to at least one carbon atom by a boron carbon bond, and at least one organic group is attached to the boron atom by the boron carbon bond.

Wherein the cyclic structure in B4 may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, hybridized forms of any one: boracycloalkanes, borabenzenes, boranaphthalenes, boraxanthenes, boraphenanthrenes, boraarenes; the listed cyclic structures are preferably borolanes, borocyclohexanes, borohexenes, borohexadienes, borohexenone, borabenzenes. Examples are:

in an embodiment of the present invention, when two or more of the structural elements are contained in the organoboron compound (I), it may be represented by the linking structure L ₃ 、L ₄ Are connected with each other; when there is only one such structural element, it may be attached to any position of the polymer chain of the non-looped or non-clustered polymer chain.

In an embodiment of the present invention, when the organoboron compound (I) contains only one of the organoboron moieties, the polymer chain may be selected from any one or any of the following: small molecule hydrocarbon groups with molecular weight not exceeding 1000Da, polymer chain residues with molecular weight greater than 1000 Da. Suitable organoboron compounds (I) formed are exemplified by the following structures:

Wherein g, h and j are each independently a fixed value or an average value, g is more than or equal to 20, h is more than or equal to 20, and j is more than or equal to 6.

The above-exemplified structures of the organoboron compound (I) are only presented for better illustration of typical structures that the organoboron compound (I) has under such conditions, but only some structures that are relatively representative under such conditions are not intended to limit the scope of the present invention.

In an embodiment of the present invention, when any one or any of two or more of the organoboron moieties described above is contained in the organoboron compound (I), the linking structure L ₂ May be selected from any one or any several of the following: a single bond, a heteroatom linker, a small divalent or multivalent molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000 Da.

When L ₃ 、L ₄ When selected from single bonds, it may be selected from boron single bonds, carbon nitrogen single bonds, nitrogen single bonds, boron carbon single bonds, boron nitrogen single bonds; l (L) ₃ 、L ₄ Preferably a boron single bond, a boron carbon single bond, and a carbon single bond. Suitable organoboron compounds (I) formed are exemplified by the following structures:

wherein h is a fixed value or an average value, and h is more than or equal to 20.

When L ₃ 、L ₄ When selected from the group consisting of heteroatom linkers, they may be selected from any one or a combination of any of the following: ether group, thio group, thioether group, divalent tertiary amine group, trivalent tertiary amine group, divalent silicon group, trivalent silicon group, tetravalent silicon group, divalent phosphorus group, trivalent phosphorus group, divalent boron group, trivalent boron group; l (L) ₃ 、L ₄ Preferred are ether groups, thio groups, divalent tertiary amine groups, trivalent tertiary amine groups. Suitable organoboron compounds (I) formed are exemplified by the following structures:

When L ₃ 、L ₄ When selected from small divalent or multivalent hydrocarbon radicals of molecular weight not exceeding 1000Da, which generally contain 1 to 71 carbon atoms, the valence of the hydrocarbon radical may be 2 to 144, which may or may not contain a heteroatom group. In general terms, the followingThe divalent or multivalent small molecule hydrocarbyl group may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: two to one hundred forty-four valence C _1-71 Alkyl, two to one hundred forty-four valence rings C _3-71 Alkyl, di-to hexavalent phenyl, di-to octavalent benzyl, di-to one hundred forty-valent aromatic hydrocarbon groups; l (L) ₃ 、L ₄ Preferably di-to tetravalent methyl, di-to hexavalent ethyl, di-to octavalent propyl, di-to hexavalent cyclopropane group, di-to octavalent cyclobutyl, di-to decavalent cyclopentyl, di-to dodecavalent cyclohexyl, di-to hexavalent phenyl. Suitable organoboron compounds (I) formed are exemplified by the following structures:

When L ₃ 、L ₄ When selected from divalent or multivalent polymer chain residues having a molecular weight greater than 1000Da, it may be any suitable divalent or multivalent polymer chain residue, including, but not limited to, divalent or multivalent carbon chain polymer residues, divalent or multivalent hetero chain polymer residues, divalent or multivalent element organic polymer residues; the polymer can be a homopolymer, a copolymer composed of any of several monomers, oligomers or polymers, and the polymer chain can be a flexible chain or a rigid chain.

When L ₃ 、L ₄ When selected from divalent or polyvalent carbon chain polymer residues, it may be any suitable polymer residue whose macromolecular backbone is predominantly comprised of carbon atoms, which may be selected from any one of the following groups, unsaturated forms of any one, taken up of any oneA substitution pattern or a hybridized pattern of either: divalent or polyvalent polyolefin chain residues such as a divalent or polyvalent polyethylene chain residue, a divalent or polyvalent polypropylene chain residue, a divalent or polyvalent polyisobutylene chain residue, a divalent or polyvalent polystyrene chain residue, a divalent or polyvalent polyvinyl chloride chain residue, a divalent or polyvalent polyvinylidene chloride chain residue, a divalent or polyvalent polyvinyl fluoride chain residue, a divalent or polyvalent polytetrafluoroethylene chain residue, a divalent or polyvalent chlorotrifluoroethylene chain residue, a divalent or polyvalent polyvinyl alcohol chain residue, a divalent or polyvalent polyvinyl alkyl ether chain residue, a divalent or polyvalent polybutadiene chain residue, a divalent or polyvalent polyisoprene chain residue, a divalent or polyvalent polychloroprene chain residue, a divalent or polyvalent polynorbornene chain residue, and the like; divalent or polyvalent polyacrylic chain residues such as divalent or polyvalent polyacrylic chain residues, divalent or polyvalent polyacrylamide chain residues, divalent or polyvalent polymethyl acrylate chain residues, divalent or polyvalent polymethyl methacrylate chain residues, and the like; divalent or polyvalent polyacrylonitrile-based chain residues, such as divalent or polyvalent polyacrylonitrile-based chain residues, and the like. L (L) ₃ 、L ₄ Divalent or multivalent polyethylene chain residues, divalent or multivalent polypropylene chain residues, divalent or multivalent polystyrene chain residues, divalent or multivalent polyvinyl chloride chain residues, divalent or multivalent polybutadiene chain residues, divalent or multivalent polyisoprene chain residues, divalent or multivalent polyacrylic chain residues, divalent or multivalent polyacrylamide chain residues, divalent or multivalent polyacrylonitrile chain residues are preferred. Suitable organoboron compounds (I) formed are exemplified by the following structures:

wherein g, h, i, j, k is a fixed value or an average value independently, preferably g.gtoreq.20, h.gtoreq.20, i.gtoreq.20, j.gtoreq.6, k.gtoreq.6.

When L ₃ 、L ₄ When selected from di-or multi-valent hetero-chain polymer residues, they may be any suitable polymer residue whose macromolecular backbone is predominantly comprised of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or polyvalent polyether chain residues such as divalent or polyvalent polyethylene oxide chain residues, divalent or polyvalent polypropylene oxide chain residues, divalent or polyvalent polytetrahydrofuran chain residues, divalent or polyvalent epoxy resin chain residues, divalent or polyvalent phenolic resin chain residues, divalent or polyvalent polyphenylene ether chain residues, etc.; divalent or multivalent polyester chain residues, such as divalent or multivalent polycaprolactone chain residues, divalent or multivalent polylactide chain residues, divalent or multivalent polyethylene terephthalate chain residues, divalent or multivalent unsaturated polyester chain residues, divalent or multivalent alkyd chain residues, divalent or multivalent polycarbonate chain residues, and the like; divalent or multivalent polyamine chain residues, such as divalent or multivalent polyamide chain residues, divalent or multivalent polyimide chain residues, divalent or multivalent polyurethane chain residues, divalent or multivalent polyurea chain residues, divalent or multivalent urea resin chain residues, divalent or multivalent melamine resin chain residues, etc. L (L) ₃ 、L ₄ Divalent or multivalent polyethylene oxide chain residues, divalent or multivalent polytetrahydrofuran chain residues, divalent or multivalent epoxy resin chain residues, divalent or multivalent polycaprolactone chain residues, divalent or multivalent polylactide chain residues, divalent or multivalent polyamide chain residues, divalent or multivalent polyurethane chain residues are preferred. Suitable organoboron compounds (I) formed are exemplified by the following structures:

When L ₃ 、L ₄ When selected from divalent or polyvalent element organic polymer residues, it may be any suitable polymer residue whose macromolecular backbone is composed primarily of inorganic element heteroatoms such as silicon, boron, aluminum, and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or multivalent organosilicon-based polymer chain residues, such as divalent or multivalent polyorganosiloxane chain residues, divalent or multivalent polyorganosiloxane nitrogen chain residues, divalent or multivalent polyorganosiloxane sulfur chain residues, divalent or multivalent polyorganosiloxane chain residues; divalent or multivalent organoboron based polymer chain residues, such as divalent or multivalent polyorganoborane chain residues, divalent or multivalent polyorganoborazine chain residues, and the like; divalent or polyvalent organophosphorus polymer chain residues; divalent or polyvalent organolead based polymer chain residues; divalent or polyvalent organotin-based polymer chain residues; divalent or polyvalent organic arsenic-based polymer chain residues; divalent or polyvalent organic antimony-based polymer chain residues. L (L) ₃ 、L ₄ Divalent or polyvalent polyorganosiloxane chain residues, and divalent or polyvalent polyorganosiloxane chain residues are preferred. Formed intoSuitable organoboron compounds (I) are exemplified by the following structures:

In embodiments of the present invention, the organoborate groups may be selected from, but are not limited to, any one or any of the following structures:

wherein K is ₂ Is a group directly attached to a boron atom selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups with molecular weight not exceeding 1000Da, polymer chain residues with molecular weight greater than 1000 Da; r is R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₆ A monovalent organic group or monovalent organosilicon group directly attached to an oxygen atom through a carbon or silicon atom, selected from any of the following structures: a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da, a small molecule silyl group having a molecular weight of no more than 1000Da, a polymer chain residue having a molecular weight of greater than 1000 Da; r is R ₅ A divalent organic group or divalent organosilicon group directly linked to two oxygen atoms, which is directly linked to an oxygen atom through a carbon atom or a silicon atom, selected from any one of the following structures: a divalent small molecular hydrocarbon group having a molecular weight of not more than 1000Da, a divalent small molecular silane group having a molecular weight of not more than 1000Da, a divalent polymer chain residue having a molecular weight of more than 1000 Da; wherein the cyclic structure in B9 is an organic compound containing at least one organic compoundThe non-aromatic or aromatic boron heterocyclic group of the borate group, the boron atom is arranged in a cyclic structure, and the cyclic structure can be a small molecular ring or a large molecular ring, and is preferably a 3-100 membered ring, more preferably a 3-50 membered ring, and still more preferably a 3-10 membered ring; the ring-forming atoms of the cyclic structure in B9 are each independently a carbon atom, a boron atom or other heteroatom, and at least one ring-forming atom is a boron atom and constitutes an organoboronate group, and at least one ring-forming atom is attached to other atoms of the compound; the hydrogen atoms on the ring atoms of the cyclic structures in B9 can be substituted or unsubstituted; the annular structure in the B9 can be a single-ring structure, a multi-ring structure, a spiro structure, a condensed ring structure, a bridge ring structure or a nested ring structure; Represents a linkage to other atoms of the compound; the boron atoms in the various structures are attached to at least one carbon atom by a boron carbon bond, and at least one organic group is attached to the boron atom by the boron carbon bond.

Wherein the cyclic structure in B9 may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: boracycloalkanes, borabenzenes, boranaphthalenes, boraxanthenes, boraphenanthrenes, boraarenes; the listed cyclic structures are preferably borolanes, borocyclohexanes, borohexenes, borohexadienes, borohexenone, borabenzenes. Examples are:

in the boron compound having an organic boric acid group and/or an organic boric acid ester group, a hydroxyl group and an ester group may be simultaneously bonded to one boron atom, and at least one boric acid group and at least one boric acid ester group may be simultaneously contained in the same module, for example:

the compound contains organic boric acid groups and organic boric acid ester groups, which is helpful for regulating and controlling the parameters such as solubility, reaction rate, reaction degree and the like, and can be used for regulating and controlling the performances such as dynamic property and the like of dynamic polymers.

In an embodiment of the present invention, when two or more of the structural elements are contained in the organoboron compound (I), it may be represented by the linking structure L ₃ 、L ₄ Interconnected, or may be attached in a pendant/side chain of a cyclic or clustered group; when there is only one such structural element, it may be attached to any position of the non-cyclic or non-clustered polymer chain.

In an embodiment of the present invention, when any one or any of two or more of the organoboron moieties described above is contained in the organoboron compound (I), the linking structure L ₃ 、L ₄ May be selected from any one or any several of the following: single bond, heteroatom linker, small divalent or multivalent molecular hydrocarbon radical with molecular weight not exceeding 1000Da, divalent or multivalent polymer chain with molecular weight greater than 1000DaA residue; the connecting structure L ₂ The selection manner of the connection structure in reference to B1, B2, B3, and B4 is not described herein, and may be exemplified as follows:

wherein g, h and j are each independently a fixed value or an average value, preferably g is more than or equal to 20, h is more than or equal to 20, and j is more than or equal to 6.

wherein K is ₃ Is a group directly attached to a boron atom selected from any one of the following structures: hydrogen atoms, heteroatom groups, aliphatic hydrocarbyloxy groups, aromatic hydrocarbyloxy groups, small molecule hydrocarbyl groups of molecular weight no more than 1000Da, polymer chain residues of molecular weight greater than 1000 Da; m is any suitable metal element or any suitable ionic group in the periodic Table of the elements, n is the valence of M, preferably +1, +2, +3, such as lithium ion, potassium ion, sodium ion, magnesium ion, calcium ion, iron ion, copper ion, ammonium ion, and the like; wherein the cyclic structure in B13 is a non-aromatic or aromatic boron heterocyclic group containing at least one organoborate group, and the boron atom is placed in the cyclic structure; the ring-forming atoms of the cyclic structure in B13 are each independently a carbon atom, a boron atom or other heteroatom, and at least one ring-forming atom is a boron atom and constitutes an organoboronate group, and at least one ring-forming atom is attached to other atoms of the compound; the boron atoms in the various structures being bonded to at least one carbon atom by a boron-carbon bond, and at least one organic group being bonded to the carbon bond by the boron-carbon bond To boron atoms;

in an embodiment of the present invention, when any one or any of two or more of the organoboron moieties described above is contained in the organoboron compound (I), the linking structure L ₃ 、L ₄ May be selected from any one or any several of the following: a single bond, a heteroatom linker, a small divalent or multivalent molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000 Da; the connecting structure L ₃ 、L ₄ The selection manner of the connection structure in reference to B1, B2, B3, and B4 is not described herein, and may be exemplified as follows:

wherein j is a fixed value or an average value, preferably j is equal to or greater than 20.

In embodiments of the present invention, the organoboron haloalkyl group may be selected from, but is not limited to, any one or any of the following structures:

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wherein K is ₄ Is a group directly attached to a boron atom selected from any one of the following structures: hydrogen atoms, heteroatom groups, aliphatic hydrocarbyloxy groups, aromatic hydrocarbyloxy groups, small molecule hydrocarbyl groups of molecular weight no more than 1000Da, polymer chain residues of molecular weight greater than 1000 Da; g ₁ ～G ₅ Each independently selected from fluorine atom, chlorine atom, bromine atom, iodine atom; wherein the cyclic structure in B17 is a non-aromatic or aromatic boron heterocyclic group containing at least one organoborate group, and the boron atom is placed in the cyclic structure; in B17The ring-forming atoms of the cyclic structure are each independently a carbon atom, a boron atom or other heteroatom, and at least one ring-forming atom is a boron atom and constitutes an organoboronate group, and at least one ring-forming atom is attached to other atoms of the compound; the boron atoms in the various structures are connected with at least one carbon atom through a boron carbon bond, and at least one organic group is connected with the boron atoms through the boron carbon bond;

in an embodiment of the present invention, when any one or any of two or more of the organoboron moieties described above is contained in the organoboron compound (I), the linking structure L ₃ 、L ₄ May be selected from any one or any several of the following: a single bond, a heteroatom linker, a small divalent or multivalent molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000 Da; the connecting structure L ₃ 、L ₄ The selection of the connection structure in reference to B1, B2, B3, B4 is not repeated here, and the structure of the suitable organoboron compound (I) formed is exemplified as follows:

In an embodiment of the present invention, in one organoboron compound (I), any one or any of the structures of an organoboron group, an organoborate group and an organoboron haloalkyl group may be contained at the same time, and the following may be exemplified in addition to the above-mentioned portions:

In an embodiment of the present invention, the dihydroxyl moiety containing compound (II) may be selected from, but is not limited to, any one or any of the following structures:

Wherein, the liquid crystal display device comprises a liquid crystal display device,represents a linkage to other atoms of the compound; r is R ₇ ～R ₉ Is a monovalent group attached to the dihydroxy moiety, each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da containing a heteroatom group, a macromolecular polymer chain residue having a molecular weight of greater than 1000 Da;

wherein L is a linking group between two carbon atoms of the dihydroxy moiety that link the hydroxy groups, and may include carbon atoms and oxygen, nitrogen, sulfur heteroatoms, the nearest number of backbone atoms that link the two hydroxy groups not exceeding 3 and not forming an m-diphenol;

wherein the heteroatom group may be selected from any of the following groups: halogen, hydroxyl, thiol, ether, thioether, carboxyl, nitro, primary, secondary, silicon, phosphorus, triazole, isoxazole, vinyl ether linkage, amide, imide, thioamide, enamine, carbonate, carbamate, thiocarbamate, thioester, orthoester a phosphate group, a phosphite group, a hypophosphite group, a phosphonate group, a phosphoryl group, a phosphino group, a thiophosphoryl group, a thiophosphorous group thiophosphinyl, phosphosilyl, silyl, carboxamide, thioamide, phosphoramide, phosphoramidite, pyrophosphamide, and cyclophosphamide, ifosfamide, thiophosphamide, aconityl, peptide bond, hydrazino, thiocarbohydrazide, azocarbohydrazide, thioazocarbohydrazide, hydrazino formate, hydrazino thiocarboxylate, carbazide, thiocarbazide, azo, isoureido, isothiourea, allophanate, thioureido formate, guanidino, amidino, aminoguanidino, aminoamidino, imido thioester, nitro, nitrosyl, sulfonic acid ester, sulfinate, sulfonamide, sulfinyl, sulfonyl hydrazino, sulfonylurea, maleimide; primary amine groups and amide groups are preferred;

Wherein when R is ₇ ～R ₉ Each independently selected from the group consisting of a small molecular hydrocarbon group having a molecular weight of not more than 1000Da, a small molecular hydrocarbon group having a molecular weight of not more than 1000Da containing a hetero atom group, having 1 to 71 carbon atoms, and the type thereof is not particularly limited, and includes but is not limited to C _1-71 Alkyl, substituted C _1-71 Alkyl, unsaturated C _1-71 Alkyl, hybridized C _1-71 Alkyl, substituted open chain heteroC _1-71 Alkyl, ring C _3-71 Alkyl, substituted ring C _3-71 Alkyl, unsaturated ring C _3-71 Alkyl, hybridized ring C _3-71 Alkyl, phenyl, benzyl, substituted phenyl, substituted benzyl, aromatic, substituted aromatic, heteroaromatic, substituted heteroaromatic; r is R ₇ ～R ₉ Preferably methyl, ethyl, propyl, propylene, butyl, butene, pentyl, hexyl, heptyl, octyl, nonyl, decyl; r is R ₇ ～R ₉ More preferably methyl, ethyl, propyl;

wherein when R is ₇ ～R ₉ Each independently selected from macromolecular polymer chains having a molecular weight greater than 1000DaWhere the residue is, it may be any suitable polymer chain residue including, but not limited to, carbon chain polymer residues, hybrid chain polymer residues, elemental organic polymer residues, where the polymer may be a homopolymer, copolymer;

wherein when R is ₇ ～R ₉ When each is independently selected from a carbon chain polymer residue, it may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: polyethylene chain residues, polypropylene chain residues, polyisobutylene chain residues, polystyrene chain residues, polyvinyl chloride chain residues, polyvinylidene chloride chain residues, polyvinyl fluoride chain residues, polytetrafluoroethylene chain residues, polytrifluoroethylene chain residues, polyacrylic acid chain residues, polyacrylamide chain residues, polymethyl acrylate chain residues, polymethyl methacrylate chain residues, polyacrylonitrile chain residues, polyvinyl alcohol chain residues, polyvinyl alkyl ether chain residues, polybutadiene chain residues, polyisoprene chain residues, polychloroprene chain residues; r is R ₇ ～R ₉ Preferably a polyethylene chain residue, a polypropylene chain residue, a polyvinyl chloride chain residue, a polyacrylic acid chain residue, a polyacrylamide chain residue, a polymethyl methacrylate chain residue, a polyvinyl alcohol chain residue;

wherein when R is ₇ ～R ₉ When each is independently selected from a heteropolymeric residue, it may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: polyether chain residues, polyester chain residues, polyethylene oxide chain residues, poly (chloromethyl) butoxy chain residues, polyphenylene ether chain residues, epoxy resin chain residues, polyethylene terephthalate chain residues, polycarbonate chain residues, unsaturated resin chain residues, alkyd resin chain residues, polyamide chain residues, polysulfone chain residues, phenolic resin chain residues, urea resin chain residues; r is R ₇ ～R ₉ Preferably polyether chain residues, polyester chain residues, polyethylene oxide chain residues, epoxy resin chain residues, polyethylene terephthalate chain residues, polycarbonate chain residues, unsaturated resin chain residues, polyamide chain residues;

wherein whenR ₇ ～R ₉ When each is independently selected from the group of elemental organic polymer residues, it may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: polyorganosiloxane chain residues, organosiloxane carbon polymer chain residues, polyalkylsiloxan chain residues, polyorganosiloxane metal silicone chain residues, polyorganosiloxane aluminum silicone chain residues, boron-containing organic polymer chain residues, polyorganosiloxane titanium silicone chain residues, polyorganosiloxane tin silicone chain residues, lead-containing polymer chain residues, polyorganosiloxane antimony silicone chain residues, polyorganosiloxane phosphorus silicone chain residues, organic fluoropolymer chain residues, organophosphorus polymer chain residues, organoboron polymer chain residues; r is R ₇ ～R ₉ Preferably polyorganosiloxane chain residues;

wherein when R is ₇ ～R ₉ When each is independently selected from a small-molecular hydrocarbon group having a molecular weight of not more than 1000Da, a small-molecular hydrocarbon group having a molecular weight of not more than 1000Da containing a hetero atom group, and a macromolecular polymer chain residue having a molecular weight of more than 1000Da, the structure thereof is not particularly limited, and may be a straight-chain type, branched type, multi-arm structure type, star type, H type, comb type, branch type, monocyclic type, polycyclic type, spiro type, condensed ring type, bridged ring type, nested ring type, chain type with a cyclic structure, two-dimensional and three-dimensional cluster type;

wherein, when L is selected from single bonds in a linear structure, the single bond refers to a carbon-carbon single bond formed between two carbon atoms connected with a hydroxyl group, and a dihydroxyl group is a 1, 2-diol group;

wherein when L is selected from a methylene group having a linear structure, the dihydroxy moiety is a 1, 3-diol moiety, and the hydrogen atom on the methylene group may be substituted with or without an optional substituent, each of the substituents independently being a hetero atom group, a small molecule hydrocarbon group having a molecular weight of not more than 1000Da containing a hetero atom group, a large molecule polymer chain residue having a molecular weight of more than 1000Da, and specific definition thereof may be referred to R ₇ ～R ₉ And will not be described in detail herein;

wherein the isomeric forms of D1-D4 are each independently selected from any one of positional isomerism, conformational isomerism, chiral isomerism;

wherein the positional isomerism comprises a positional isomerism structure resulting from the difference in the positions of substituents, functional groups or linking groups on the dihydroxy moieties. For example, when R ₇ ～R ₈ When selected from the same substituents, the positional isomeric structure of D2 may be:

similarly, D1 to D4 also have their positional isomerism;

wherein the conformational isomerism comprises a conformational isomerism structure generated by various arrangements of atoms in space caused by rotation of the intramolecular around the bond;

wherein the chiral isomers comprise chiral isomeric structures that are mirror images of each other. Taking the example of L being selected from carbon-carbon single bonds, when both carbon atoms of the 1, 2-diol moiety are chiral carbon atoms, the stereoisomeric structure of D1 may be:

similarly, D2 to D4 have chiral structures.

The above-mentioned heterogeneous structure is only presented for better understanding of the typical structure possessed by this condition, and is not intended to limit the scope of the present invention.

Wherein when L is selected from an aliphatic ring, at least one of the two carbon atoms directly attached to the two hydroxyl groups participates in the ring formation, when both carbon atoms participate in the ring formation, the formed dihydroxy moiety is a 1, 2-diol moiety, and when only one carbon atom participates in the ring formation, the formed dihydroxy moiety is a 1, 3-diol moiety; the cyclic structure is a 3-to 200-membered ring, preferably a 3-to 50-membered ring, more preferably a 3-to 10-membered ring, and the number of the cyclic structures is 1,2 or more; it may be any alicyclic or alicyclic ring, and each ring forming atom is independently a carbon atom or a heteroatom; the said process The hetero atom may be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, boron atom; the hydrogen atom on the alicyclic ring-forming atom may be substituted with any substituent or may be unsubstituted; the substituents are each independently a heteroatom group, a small molecular hydrocarbon group having a molecular weight of not more than 1000Da containing a heteroatom group, a macromolecular polymer chain residue having a molecular weight of more than 1000Da, the definition of which can be referred to R ₁ ～R ₃ And will not be described in detail here. In general, the alicyclic and alicyclic rings include, but are not limited to, ring C _3-200 An alkane, an oxirane, an azetidine, a squaric acid, a cyclobutanedione, a hemi-squaric acid, a metallocene, a tetrahydrofuran, a pyrrolidine, a thiazolidine, a dihydroisoxazole, an oxazolidine, a cyclohexene, a tetrahydropyran, a piperidine, a 1, 4-dioxane, a norbornane, a norbornene, a norbornadiene, a 1,4, 7-triazacyclononane, a cyclocycloning, a furan, a thiophene, a pyrrole, an imidazole, an oxazole, an isoxazole, a thiazole, an isothiazole, a pyrazole, a caprolactone, and the like; the alicyclic and alicyclic heterocyclic ring is preferably cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, ethylene oxide, furan, thiophene and pyrrole; the alicyclic and alicyclic heterocyclic rings are more preferably cyclopropane, cyclobutane, cyclopentane, cyclohexane. Examples are:

Wherein, when L is selected from aromatic ring, at least one of two carbon atoms directly connected with two hydroxyl groups participates in ring formation, when both carbon atoms participate in ring formation, the formed dihydroxy moiety is an ortho-diphenol hydroxyl moiety, and when only one carbon atom participates in ring formation, the formed dihydroxy moiety is a 2-hydroxymethyl phenol hydroxyl moiety; the cyclic structure is a 3-to 200-membered ring, preferably a 3-to 50-membered ring, more preferably a 3-to 10-membered ring, and the number of the cyclic structures is 1, 2 or more; it may be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are each independently a carbon atom or a heteroatom; when both hydroxyl groups are directly bonded to the aromatic ring, the positional relationship of the two hydroxyl groupsIs ortho; the hetero atom may be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted; the substituents are each independently a heteroatom group, a small molecular hydrocarbon group having a molecular weight of not more than 1000Da containing a heteroatom group, a macromolecular polymer chain residue having a molecular weight of more than 1000Da, the definition of which can be referred to R ₁ ～R ₃ And will not be described in detail here.

The aromatic ring is a polyene compound with a coplanar cyclic closed conjugated system, and the pi electron number of the compound meets the general formula 4n+2 (n is a natural number).

The pi electrons are electrons participating in bonding by using P orbit electrons, wherein the P orbit is an atomic orbit, the angular quantum number is 1, the magnetic quantum number can be-1, 0 or +1, three P orbits are arranged in each P shell layer, and Px, py and Pz are identical in shape but different in direction, and can accommodate 2 electrons, so that the P orbits can accommodate 6 electrons at most. In general, there are 2 pi electrons per double bond and 4 pi electrons per triple bond.

In general terms, the aromatic ring or heteroaromatic ring includes, but is not limited to, benzene ring, pyridine, pyridazine, pyrimidine, pyrazine, 1,3, 5-triazine, indene, indane, indole, isoindole, purine, naphthalene, anthracene, dihydroanthracene, xanthene (xanthene), thioxanthene, phenanthrene, dihydrophenanthrene, 10, 11-dihydro-5H-dibenzo [ a, d ] cycloheptane, dibenzocycloheptene, 5-dibenzocycloheptenone, quinoline, isoquinoline, fluorene, carbazole, iminodibenzyl, naphthalene ethyl ring, dibenzocyclooctyne, azadibenzocyclooctyne, and the like; the aromatic ring or aromatic heterocyclic ring is preferably benzene ring or pyridine. Examples are:

When the cyclic structure is selected from an aliphatic ring, an aromatic ring, and a cyclic structure containing both an aliphatic ring and an aromatic ring, the structure thereof is not particularly limited. It may be a monocyclic structure, i.e. a structure containing only one ring, for example:

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it may be a polycyclic structure, i.e. a structure containing two or more independent rings, for example:

it may be a spiro structure, i.e., a structure containing a cyclic structure composed of two or more rings sharing one atom with each other, for example:

there may be mentioned condensed ring structures (including bicyclic and aromatic ring structures), that is, structures containing a cyclic structure composed of two or more rings sharing two adjacent atoms with each other, such as, for example:

the bridged ring structure may be one in which two or more rings are formed by sharing two or more adjacent atoms with each other, such as:

it may be a nested ring structure, i.e. a structure comprising two or more rings connected or nested with each other, for example:

or a combination of any of the above cyclic structures.

The following two examples are given as descriptions of structures which the cyclic structure has when selected from the group consisting of cyclic structures containing dihydroxy moieties.

For example, when the cyclic structure is selected from cyclopropane, it is selected from any one of the following structures or isomeric forms thereof:

wherein each of the isomeric forms E1 to E4 is independently selected from any one of positional isomerism, conformational isomerism, cis-trans isomerism and chiral isomerism.

Wherein the positional isomerism structure comprises a positional isomerism structure generated by different positions of a substituent, a functional group or a connecting group on a cyclic structure of a 1, 2-diol primitive. For example, the positional isomerism of E1 may be

Similarly, E2 to E4 also have their positional isomerism;

wherein the cis-trans isomerism structure comprises a cis-trans isomerism structure generated by restricting free rotation of sigma bonds due to the existence of a ring. For example, the cis-trans isomerism structure of E1 may be

Similarly, E2 to E4 also have cis-trans isomerism structures;

wherein the conformational isomerism structure comprises a conformational isomerism structure generated by various arrangements of atoms in space caused by rotation of a bond in a molecule. For example, the conformational isomerism structure of E1 may be

Similarly, E2 to E4 also have their conformational isomerism structure;

wherein the chiral heterogeneous structure comprises chiral heterogeneous structures which are mirror images of each other. For example, the stereoisomeric structure of E1 may be

Similarly, E2 to E4 also have chiral heterogeneous structures;

for another example, when the cyclic structure is selected from benzene rings, it is selected from any one of the following structures or their positional isomeric structures:

wherein the positional isomerism structure comprises a positional isomerism structure generated by the difference of the positions of the substituent, the functional group or the connecting group on the ring forming atom of the cyclic structure where the 1, 3-diol moiety is located and on the carbon atom of the 1, 3-diol moiety. For example, the positional isomerism of F1 may be

Similarly, F2 to F6 also have their positional isomerism;

The two or more dihydroxy moieties may be interconnected to form a polyol compound by a linker T which may be selected from any one or more of the following: a single bond or unsaturated bond, a heteroatom linker, a divalent or multivalent small molecule hydrocarbyl radical having a molecular weight of no more than 1000Da containing a heteroatom group, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000Da, a divalent or multivalent inorganic macromolecule having a molecular weight of greater than 1000 Da. At this time, a suitable dihydroxy moiety-containing compound (II) structure is formed as follows:

Wherein g is a fixed value or an average value, and g is more than or equal to 36.

The above-exemplified dihydroxy-moiety-containing compound (II) is only provided for better illustration of the structure of the dihydroxy-moiety-containing compound (II) under such conditions, and the typical structures proposed are only some of the most representative structures under such conditions, and are not intended to limit the scope of the present invention.

When T is selected from a single bond or an unsaturated bond, it is selected from any one of the following structures: a carbon-carbon single bond, a carbon-nitrogen single bond, a nitrogen-nitrogen single bond, a carbon-carbon double bond, and an aromatic group; carbon-carbon single bonds are preferred. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

When T is selected from a heteroatom linker, it may be selected from any one or a combination of any of the following: ether, thioether, secondary amine, tertiary amine, silicon, phosphorus, triazole, isoxazole, triazine, vinyl ether linkage, amide, imide, thioamide, enamine, carbonate, carbamate, thiocarbamate, thioester, orthoester, phosphate, phosphite, phosphinate, phosphonate, phosphoryl, phosphido, thiophosphoryl, thiophosphinyl, phospho, phosphosilane, silane, carboxamide, thioamide, phosphoramidite, pyrophosphamide, cyclophosphamide, ifosfamide, cyclophosphamide, and the like thiophosphamide, aconityl, peptide bond, thioamide bond, hydrazino, hydrazide, thiocarbohydrazide, azocarbohydrazide, thioazocarbohydrazide, hydrazino formate, hydrazino thiocarboxylate, carbazide, thiocarbazide, azo, isourea, isothiourea, allophanate, thiouroformate, guanidine, amidino, aminoguanidine, amimidino, imido, imidothioate, nitroxyl, nitrosyl, sulfonic acid ester, sulfinate, sulfonamide, sulfinamide, sulfonyl, sulfonylurea, maleimide; the heteroatom linking group is preferably an ether group, a thioether group, a secondary amine group, a tertiary amine group, an amide group, a carbonate group, a carbamate group, or a urea group. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

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When T is selected from a divalent or multivalent small molecule hydrocarbyl radical of molecular weight no more than 1000Da or a divalent or multivalent small molecule hydrocarbyl radical containing a heteroatom radical of molecular weight no more than 1000Da, it has from 1 to 71 carbon atoms and the valence of the hydrocarbyl radical is from 2 to 144, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybridized forms of any one: two to one hundred forty-four valence C _1-71 Alkyl, two toOne hundred forty-four tetravalent ring C _3-71 Alkyl, di-to hexavalent phenyl, di-to octavalent benzyl, di-to one hundred forty-valent aromatic hydrocarbon groups; t is preferably a di-to tetravalent methyl group, a di-to hexavalent ethyl group, a di-to octavalent propyl group, a di-to hexavalent cyclopropane group, a di-to octavalent cyclobutyl group, a di-to decavalent cyclopentyl group, a di-to dodecavalent cyclohexyl group, or a di-to hexavalent phenyl group. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

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When T is selected from small molecule hydrocarbon groups with the molecular weight of not more than 1000Da containing heteroatom groups, the small molecule hydrocarbon groups can contain any one or more than one of the following heteroatom groups: halogen, hydroxyl, thiol, ether, thioether, carboxyl, nitro, primary, secondary, silicon, phosphorus, triazole, isoxazole, vinyl ether linkage, amide, imide, thioamide, enamine, carbonate, carbamate, thiocarbamate, thioester, orthoester phosphate, phosphite, hypophosphite, phosphonate, phosphoryl, phosphites, hypophosphite, thiophosphoryl, thiophosphite, thiophosphinyl, phosphosilane, silane ester, carboxamide, thioamide, phosphoramide, phosphoramidite, pyrophosphamide, cyclophosphamide, and ifosfamide, thiophosphamide, aconityl, peptide bond, thioamide bond, hydrazino, thiocarbohydrazide, azocarbohydrazide, thioazocarbohydrazide, hydrazino formate, hydrazino thiocarbazide, azo, isoureido, isothiourea, allophanate, thiouroformate, guanidine, amidino, aminoguanidine, aminoamidino, imido thioester, nitro, nitrosyl, sulfonic acid ester, sulfinate, sulfonamide, sulfinylamino, sulfonyl, sulfonylurea, maleimide.

When T is selected from a divalent or multivalent polymer chain residue having a molecular weight greater than 1000Da, it may be any suitable divalent or multivalent polymer chain residue, including but not limited to a divalent or multivalent carbon chain polymer residue, a divalent or multivalent hetero chain polymer residue, a divalent or multivalent element organic polymer residue; wherein the polymer can be a homopolymer or a copolymer;

when T is selected from a divalent or multivalent carbon chain polymer residue, it may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: divalent or multivalent polyethylene chain residues, divalent or multivalent polypropylene chain residues, divalent or multivalent polyisobutylene chain residues, divalent or multivalent polystyrene chain residues, divalent or multivalent polyvinyl chloride chain residues, divalent or multivalent polyvinylidene chloride chain residues, divalent or multivalent polytetrafluoroethylene chain residues, divalent or multivalent polytrifluoroethylene chain residues, divalent or multivalent polyacrylic acid chain residues, divalent or multivalent polyacrylamide chain residues, divalent or multivalent polymethyl acrylate chain residues, divalent or multivalent polymethyl methacrylate chain residues, divalent or multivalent polyacrylonitrile chain residues, divalent or multivalent polyvinyl alcohol chain residues, divalent or multivalent polyvinyl alkyl ether chain residues, divalent or multivalent polybutadiene chain residues, divalent or multivalent polyisoprene chain residues, divalent or multivalent polychloroprene chain residues; t is preferably a divalent or polyvalent polyethylene chain residue, a divalent or polyvalent polypropylene chain residue, a divalent or polyvalent polyvinyl chloride chain residue, a divalent or polyvalent polyacrylamide chain residue, a divalent or polyvalent polymethyl acrylate chain residue, a divalent or polyvalent polymethyl methacrylate chain residue. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

Wherein g and h are each independently a fixed value or an average value, g is more than or equal to 36, and h is more than or equal to 10.

When T is selected from a divalent or multivalent heteropolymeric polymer residue, it can be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: divalent or multivalent polyether chain residues, divalent or multivalent polyester chain residues, divalent or multivalent polyethylene oxide chain residues, divalent or multivalent poly (chloromethyl) butoxy chain residues, divalent or multivalent polyphenylene ether chain residues, divalent or multivalent epoxy resin chain residues, divalent or multivalent polyester resin chain residues, divalent or multivalent polycarbonate chain residues, divalent or multivalent unsaturated resin chain residues, divalent or multivalent alkyd resin chain residues, divalent or multivalent polyamide chain residues, divalent or multivalent phenolic resin chain residues, divalent or multivalent urea resin chain residues; t is preferably a divalent or polyvalent polyether chain residue, a divalent or polyvalent polyester chain residue, a divalent or polyvalent polyethylene oxide chain residue, a divalent or polyvalent epoxy resin chain residue, a divalent or polyvalent polyethylene terephthalate chain residue, a divalent or polyvalent polycarbonate chain residue, a divalent or polyvalent unsaturated resin chain residue, a divalent or polyvalent polyamide chain residue. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

Wherein h is a fixed value or an average value, and h is more than or equal to 10.

When T is selected from a divalent or multivalent element organic polymer residue, it may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: divalent or multivalent polyorganosiloxane chain residues, divalent or multivalent organosiloxane carbon polymer chain residues, divalent or multivalent polyalkylsiloxanyl chain residues, divalent or multivalent polyorganosiloxane chain residues, divalent or multivalent polyaluminosiloxane chain residues, divalent or multivalent boron-containing organic polymer chain residues a divalent or multivalent polyorganosiloxane chain residue, a divalent or multivalent lead-containing polymer chain residue, a divalent or multivalent polyorganosiloxane chain residue, a divalent or multivalent organic fluoropolymer chain residue, a divalent or multivalent organophosphorus polymer chain residue, a divalent or multivalent organoboron polymer chain residue; t is preferably a divalent or polyvalent polyorganosiloxane chain residue. Suitable dihydroxy moiety-containing compounds (II) are formed, for example, as follows:

Wherein g is a fixed value or an average value, and g is more than or equal to 15.

When T is selected from a divalent or multivalent inorganic macromolecule having a molecular weight greater than 1000Da, it may be selected from any one of the following groups or surface modification products of any one of the following groups: polysilanes, zeolite-type molecular sieves, aluminum phosphate molecular sieves, zirconium phosphate molecular sieves, heteropolyacid salt molecular sieves, diamond, graphite, graphene oxide, carbon nanotubes, fullerenes, carbon fibers, white phosphorus, red phosphorus, phosphorus pentoxide, polyphosphoric acid, polyphosphazenes, polychlorophosphazenes, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talc, kaolin, montmorillonite, mica, asbestos, cement, glass fibers, ceramic, boron oxide, sulfur nitride, calcium silicide, beryllium oxide, magnesium oxide, mercury oxide, borohydride, boron nitride, boron carbide, aluminum nitride, diaspore, gibbsite, corundum, titania, phthalocyanine polymers; t is preferably surface-modified graphene, surface-modified carbon fiber, surface-modified silica, surface-modified glass fiber.

When T is selected from a divalent or polyvalent small molecular hydrocarbon group having a molecular weight of not more than 1000Da, a divalent or polyvalent small molecular hydrocarbon group having a molecular weight of not more than 1000Da containing a hetero atom group, a divalent or polyvalent polymer chain residue having a molecular weight of more than 1000Da, the structure thereof is not particularly limited, and may be a straight chain type, a branched chain type, a multi-arm structure type, a star type, an H type, a comb type, a branch type, a monocyclic type, a polycyclic type, a spiro type, a condensed ring type, a bridged ring type, a nested ring type, a chain type with a ring structure, a two-dimensional and three-dimensional network type.

In particular, suitable compounds (II) containing dihydroxy moieties formed by forming a polyol compound by sharing one carbon atom, sharing one single carbon-carbon bond or sharing one double carbon-carbon bond between two or more dihydroxy moieties are exemplified by the following structures:

In an embodiment of the present invention, the monohydroxy moiety-containing compound (III) includes, but is not limited to, a compound containing a monoalkyl alcohol moiety, a monoalkol moiety, a monophenol hydroxy moiety, and a polyhydroxy compound containing a polyphenol hydroxy moiety in the meta position, a polyphenol hydroxy moiety in the para position, and a hydroxy group separated by at least four atoms. When compound (III) contains only one monohydroxyl moiety, it may be selected from, but is not limited to, any of the following structures:

Wherein R is ₁₀ ～R ₁₁ Is a monovalent group attached to a monohydroxyl moiety, each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da containing a heteroatom group, a macromolecular polymer chain residue having a molecular weight of greater than 1000 Da; specific definition of the compound can refer to substituent R in the dihydroxyl motif structure ₇ ～R ₉ The selection of (2) is not described in detail herein; wherein, the cyclic structure in M4 and M5 is a non-aromatic or aromatic ring group containing at least one hydroxyl group, and carbon atoms are arranged in the cyclic structure, and the cyclic structure can be a small molecular ring or a large molecular ring, and is preferably a 3-100 membered ring, more preferably a 3-50 membered ring, and more preferably a 3-10 membered ring; the ring-forming atoms of the cyclic structures in M4, M5 are each independently a carbon atom, a silicon atom, an oxygen atom or other heteroatom; the hydrogen atoms on the ring atoms of the ring structures in M4 and M5 can be substituted or not substituted; the annular structures in M4 and M5 can be a single-ring structure, a multi-ring structure, a spiro structure, a condensed ring structure, a bridged ring structure and a nested ring structure; examples are:

wherein, the liquid crystal display device comprises a liquid crystal display device,represents the attachment of a polymer chain, cross-linking or any other suitable group (including hydrogen atoms);

In the present invention, when the compound containing a monohydroxyl moiety is present in the polymer and there are two or more of the linkages, it may be linked in a non-cyclic or non-clustered polymer chain, or in a cyclic or clustered side/side chain; when there is only one such linkage, it can be attached to any position of the polymer chain. Suitable compounds (III) containing a monohydroxyl moiety are formed, for example, as follows:

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wherein g and h are each independently a fixed value or an average value, g is more than or equal to 15, and h is more than or equal to 10.

The above-exemplified monohydroxy-group-containing compound (III) is only provided for better illustration of the typical structure of the monohydroxy-group-containing compound (III) under such conditions, and is only a representative structure under such conditions, and is not intended to limit the scope of the present invention.

In an embodiment of the present invention, the compound (III) containing a monohydroxy moiety includes, but is not limited to, a compound containing a monoalkyl alcohol moiety, a monoalkol moiety, a monophenol hydroxy moiety, and a polyhydroxy compound containing a polyphenol hydroxy moiety in the meta position, a polyphenol hydroxy moiety in the para position, and a hydroxy group separated by at least four atoms. When the compound (III) contains two or more monohydroxyl moieties, the two or more monohydroxyl moieties may be linked through a linking group, and the monohydroxyl moiety may be any one or more of M1, M2, M3, M4, and M5, to form a structure such as M6, M7, or M8:

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wherein R is ₁₂ ～R ₁₃ Is a monovalent group attached to a monohydroxyl moiety, each independently selected from the group consisting of a hydrogen atom, a heteroatom group, a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da containing a heteroatom group, a macromolecular polymer chain residue having a molecular weight of greater than 1000 Da; specific definition of the compounds may refer to the substituents R in the dihydroxy moieties ₇ ～R ₉ The selection of (2) is not described in detail herein;

wherein L is ₁ 、L ₂ For the connection of the linking group between two monohydroxyl moieties, any one or any several structures selected from the group consisting of linear structures, aliphatic ring structures, aliphatic heterocyclic structures, aromatic ring structures and aromatic heterocyclic structures may be used.

When L ₁ 、L ₂ When any one or any of the structures is selected from an aliphatic ring structure, an aliphatic heterocyclic structure, an aromatic ring structure and an aromatic heterocyclic structure, a carbon atom connected to a hydroxyl group may or may not participate in ring formation.

Specifically, L ₁ 、L ₂ May be selected from any one or any several of the following: a single bond or an unsaturated bond, a heteroatom linker, a divalent or multivalent small molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000Da, a divalent or multivalent inorganic small molecule chain residue having a molecular weight of no more than 1000Da, a divalent or multivalent inorganic large molecule chain residue having a molecular weight of greater than 1000 Da.

When L ₁ 、L ₂ When selected from single bonds or unsaturated bonds, it is selected from any one of the following structures: a carbon-carbon single bond, a carbon-nitrogen single bond, a nitrogen-nitrogen single bond, a carbon-carbon double bond, and an aromatic group; excellent (excellent)And selecting carbon-carbon single bonds. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

When L ₁ 、L ₂ When selected from the group consisting of heteroatom linkers, may be selected from any one or a combination of any of the following: ether, thioether, secondary amine, tertiary amine, silicon, phosphorus, triazole, isoxazole, triazine, vinyl ether linkage, amide, imide, thioamide, enamine, carbonate, carbamate, thiocarbamate, thioester, orthoester, phosphate, phosphite, phosphinate, phosphonate, phosphoryl, phosphido, thiophosphoryl, thiophosphinyl, phospho, phosphosilane, silane, carboxamide, thioamide, phosphoramidite, pyrophosphamide, cyclophosphamide, ifosfamide, cyclophosphamide, and the like thiophosphamide, aconityl, peptide bond, thioamide bond, hydrazino, hydrazide, thiocarbohydrazide, azocarbohydrazide, thioazocarbohydrazide, hydrazino formate, hydrazino thiocarboxylate, carbazide, thiocarbazide, azo, isourea, isothiourea, allophanate, thiouroformate, guanidine, amidino, aminoguanidine, amimidino, imido, imidothioate, nitroxyl, nitrosyl, sulfonic acid ester, sulfinate, sulfonamide, sulfinamide, sulfonyl, sulfonylurea, maleimide; l (L) ₁ 、L ₂ Preferred are ether groups, thioether groups, secondary amine groups, tertiary amine groups, amide groups, carbonate groups, carbamate groups, urea groups. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

When L ₁ 、L ₂ When selected from small divalent or multivalent hydrocarbon radicals of molecular weight not exceeding 1000Da, which generally contain 1 to 71 carbon atoms, the valence of the hydrocarbon radical may be 2 to 144, which may or may not contain a heteroatom group. In general terms, the divalent or multivalent small molecule hydrocarbyl group may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: two to one hundred forty-four valence C _1-71 Alkyl, two to one hundred forty-four valence rings C _3-71 Alkyl, di-to hexavalent phenyl, di-to octavalent benzyl, di-to one hundred forty-valent aromatic hydrocarbon groups; l (L) ₁ 、L ₂ Preferably di-to tetravalent methyl, di-to hexavalent ethyl, di-to octavalent propyl, di-to hexavalent cyclopropane group, di-to octavalent cyclobutyl, di-to decavalent cyclopentyl, di-to dodecavalent cyclohexyl, di-to hexavalent phenyl. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

Wherein g is a fixed value or an average value, and g is more than or equal to 20.

When L ₁ 、L ₂ Selected from molecular weights greater thanWhen a divalent or multivalent polymer chain residue of 1000Da, it may be any suitable divalent or multivalent polymer chain residue, including but not limited to divalent or multivalent carbon chain polymer residues, divalent or multivalent hetero chain polymer residues, divalent or multivalent element organic polymer residues. Wherein, the polymer can be a homopolymer or a copolymer composed of any of several monomers, oligomers or polymers; the polymer chains may be flexible chains or rigid chains.

When L ₁ 、L ₂ When selected from a divalent or multivalent carbon chain polymer residue, it may be any suitable polymer residue whose macromolecular backbone is composed primarily of carbon atoms, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or polyvalent polyolefin chain residues such as a divalent or polyvalent polyethylene chain residue, a divalent or polyvalent polypropylene chain residue, a divalent or polyvalent polyisobutylene chain residue, a divalent or polyvalent polystyrene chain residue, a divalent or polyvalent polyvinyl chloride chain residue, a divalent or polyvalent polyvinylidene chloride chain residue, a divalent or polyvalent polyvinyl fluoride chain residue, a divalent or polyvalent polytetrafluoroethylene chain residue, a divalent or polyvalent chlorotrifluoroethylene chain residue, a divalent or polyvalent polyvinyl alcohol chain residue, a divalent or polyvalent polyvinyl alkyl ether chain residue, a divalent or polyvalent polybutadiene chain residue, a divalent or polyvalent polyisoprene chain residue, a divalent or polyvalent polychloroprene chain residue, a divalent or polyvalent polynorbornene chain residue, and the like; divalent or polyvalent polyacrylic chain residues such as divalent or polyvalent polyacrylic chain residues, divalent or polyvalent polyacrylamide chain residues, divalent or polyvalent polymethyl acrylate chain residues, divalent or polyvalent polymethyl methacrylate chain residues, and the like; divalent or polyvalent polyacrylonitrile-based chain residues, such as divalent or polyvalent polyacrylonitrile-based chain residues, and the like. L (L) ₁ 、L ₂ Preferably a divalent or polyvalent polyethylene chain residue, a divalent or polyvalent polypropylene chain residue, a divalent or polyvalent polystyrene chain residue, a divalent or polyvalent polyvinyl chloride chain residue, a divalent or polyvalent polybutadiene chain residue, a divalent or polyvalent polyisoprene chain residue, a divalent or polyvalent polyacrylic chain residue, a divalent or polyvalent polyacrylamide chain residue, a divalent or polyvalent poly (vinyl chloride) chain residue, a divalent or polyvalent poly (acrylic acid) chain residue, a divalent or polyvalent poly (acrylamide) chain residue,Divalent or polyvalent polyacrylonitrile chain residues. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

wherein g, h, i, j, k is a fixed value or an average value independently, preferably g is not less than 36, h is not less than 36, i is not less than 36, j is not less than 12, and k is not less than 12.

When L ₁ 、L ₂ When selected from di-or multi-valent hetero-chain polymer residues, they may be any suitable polymer residue whose macromolecular backbone is predominantly comprised of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or polyvalent polyether chain residues such as divalent or polyvalent polyethylene oxide chain residues, divalent or polyvalent polypropylene oxide chain residues, divalent or polyvalent polytetrahydrofuran chain residues, divalent or polyvalent epoxy resin chain residues, divalent or polyvalent phenolic resin chain residues, divalent or polyvalent polyphenylene ether chain residues, etc.; divalent or multivalent polyester chain residues, such as divalent or multivalent polycaprolactone chain residues, divalent or multivalent polylactide chain residues, divalent or multivalent polyethylene terephthalate chain residues, divalent or multivalent unsaturated polyester chain residues, divalent or multivalent alkyd chain residues, divalent or multivalent polycarbonate chain residues, and the like; divalent or multivalent polyamine chain residues, such as divalent or multivalent polyamide chain residues, divalent or multivalent polyimide chain residues, divalent or multivalent polyurethane chain residues, divalent or multivalent polyurea chain residues, divalent or multivalent urea resin chain residues, divalent or multivalent melamine resin chain residues, etc. L (L) ₁ 、L ₂ Preferably divalent or polyvalent polyEthylene oxide chain residues, divalent or multivalent polytetrahydrofuran chain residues, divalent or multivalent epoxy resin chain residues, divalent or multivalent polycaprolactone chain residues, divalent or multivalent polylactide chain residues, divalent or multivalent polyamide chain residues, divalent or multivalent polyurethane chain residues. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

When L ₁ 、L ₂ When selected from divalent or polyvalent element organic polymer residues, it may be any suitable polymer residue whose macromolecular backbone is composed primarily of inorganic element heteroatoms such as silicon, boron, aluminum, and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or multivalent organosilicon-based polymer chain residues, such as divalent or multivalent polyorganosiloxane chain residues, divalent or multivalent polyorganosiloxane nitrogen chain residues, divalent or multivalent polyorganosiloxane sulfur chain residues, divalent or multivalent polyorganosiloxane chain residues; divalent or multivalent organoboron based polymer chain residues, such as divalent or multivalent polyorganoborane chain residues, divalent or multivalent polyorganoborazine chain residues, and the like; divalent or polyvalent organophosphorus polymers A compound chain residue; divalent or polyvalent organolead based polymer chain residues; divalent or polyvalent organotin-based polymer chain residues; divalent or polyvalent organic arsenic-based polymer chain residues; divalent or polyvalent organic antimony-based polymer chain residues. L (L) ₁ 、L ₂ Divalent or polyvalent polyorganosiloxane chain residues, and divalent or polyvalent polyorganosiloxane chain residues are preferred. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

wherein g, h, i, k is a fixed value or an average value independently, preferably g is not less than 36, h is not less than 36, i is not less than 36, and k is not less than 12.

When L ₁ 、L ₂ When selected from divalent or multivalent inorganic small molecule chain residues having a molecular weight of not more than 1000Da, they may be any suitable inorganic small molecule chain residues having a molecular main chain and side chains consisting essentially of inorganic element heteroatoms such as silicon, boron, aluminum, and the like and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus, and the like, and in general terms, the divalent or multivalent inorganic small molecule chain residues may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybridized forms of any one: a divalent or multivalent silane chain residue, a divalent or multivalent silicon compound chain residue, a divalent or multivalent sulfur nitrogen compound chain residue, a divalent or multivalent phosphazene compound chain residue, a divalent or multivalent phosphorus oxide compound chain residue, a divalent or multivalent borane chain residue, a divalent or multivalent boron oxide compound chain residue. L (L) ₁ 、L ₂ Preferably, a divalent or polyvalent silane chain residue, a divalent or polyvalent silicon compound chain residue, a divalent or polyvalent phosphazene compound chain residueDivalent or polyvalent borane chain residues. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

When L ₁ 、L ₂ When selected from divalent or polyvalent inorganic macromolecular chain residues with a molecular weight of more than 1000Da, the residues can be any suitable inorganic macromolecular chain residues with main chains and side chains of macromolecules mainly composed of inorganic element heteroatoms such as silicon, boron, aluminum and the like and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and the like.

Wherein L is ₁ 、L ₂ An unsaturated form, a substituted form, or a hybridized form of any one selected from the group consisting of: divalent or multivalent polysilane chain residues, divalent or multivalent polysiloxane chain residues, divalent or multivalent polysulfide silicon chain residues, divalent or multivalent polysulfide nitrogen chain residues, divalent or multivalent polyphosphate chain residues, divalent or multivalent polyphosphazene chain residues, divalent or multivalent polychlorophosphazene chain residues, divalent or multivalent polyborophosphazene chain residues, divalent or multivalent polyborone chain residues. L (L) ₁ 、L ₂ Divalent or polyvalent polysilane chain residues, divalent or polyvalent polysiloxane chain residues, divalent or polyvalent polyphosphazene chain residues, divalent or polyvalent polyborane chain residues are preferred. Suitable structures of the monohydrocarbon-containing hydroxyl compounds (III) formed are exemplified below:

wherein g and h are each independently a fixed value or an average value, preferably g is more than or equal to 36 and h is more than or equal to 36.

L ₁ 、L ₂ The inorganic macromolecule with residue can also be selected from any one of the following groups or any inorganic macromolecule with residue which is subjected to surface modification: zeolite molecular sieves, aluminum phosphate molecular sieves, zirconium phosphate molecular sieves, heteropolyacid salt molecular sieves, diamond, graphite, graphene oxide, carbon nanotubes, fullerenes, carbon fibers, white phosphorus, red phosphorus, phosphorus pentoxide, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talc, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramic, boron oxide, sulfur nitride, calcium silicide, silicate, glass fibers, beryllium oxide, magnesium oxide, mercury oxide, borohydride, boron nitride, boron carbide, aluminum nitride, diaspore, gibbsite, corundum, titanium dioxide. L (L) ₁ 、L ₂ Preferably surface modified graphene, surface modified carbon fiber, surface modified silica, surface modified silicon nitride, surface modified silicon carbide, surface modified silicate, surface modified glass fiber, surface modified boron nitride. Suitable monohydroxy-containing compounds formed are generally inorganic structures, such as, for example: silicon nitride with silicon hydroxyl on the surface, silicon carbide with silicon hydroxyl on the surface, silicon dioxide with silicon hydroxyl on the surface, silicate with silicon hydroxyl on the surface, and glass fiber with silicon hydroxyl on the surface.

Wherein L is ₀ For the connection of the linking group between two monohydroxyl moieties, any one or any several structures selected from the group consisting of linear structures, aliphatic ring structures, aliphatic heterocyclic structures, aromatic ring structures and aromatic heterocyclic structures; the specific selection method refers to L ₁ 、L ₂ The selection method of (2) is not described in detail here; and L is equal to ₁ 、L ₂ Except for L ₀ Containing at least two backbone atoms, forming a suitable groupThe structure of the monohydrocarbon hydroxy compound (III) is exemplified as follows:

/>

wherein g, h, i, j, k is a fixed value or an average value independently, preferably g is not less than 36, h is not less than 36, i is not less than 36, j is not less than 36, and k is not less than 12.

In an embodiment of the present invention, the compound (IV) containing a silylhydroxy/silylhydroxy precursor may be selected from, but is not limited to, the following structures:

wherein K is ₅ 、K ₆ 、K ₇ 、K ₈ 、K ₉ 、K ₁₀ 、K ₁₁ 、K ₁₂ 、K ₁₃ 、K ₁₄ Is a group directly attached to a silicon atom, each of which is independently selected from any one of the following structures: a hydrogen atom, a heteroatom group, a small molecular hydrocarbon group with a molecular weight of not more than 1000Da, a polymer chain residue with a molecular weight of more than 1000Da, an inorganic small molecular chain residue with a molecular weight of not more than 1000Da, an inorganic large molecular chain residue with a molecular weight of more than 1000 Da; a is that ₁ 、A ₂ 、A ₃ 、A ₄ 、A ₅ 、A ₆ 、A ₇ 、A ₈ 、A ₉ 、A ₁₀ 、A ₁₁ 、A ₁₂ 、A ₁₃ 、A ₁₄ Hydrolyzable groups directly bonded to the silicon atom include, but are not limited to, halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide, preferably halogen, alkoxy; wherein the cyclic structure in C7, C8, C9, C16, C17 and C18 is a non-aromatic or aromatic silicon heterocyclic group containing at least one silicon hydroxyl group, and the silicon atom is arranged in the cyclic structure, and the cyclic structure can be a small molecular ring or a large molecular ring, and is preferably a 3-100-membered ring, more preferably a 3-50-membered ring, and even more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic structures in C7, C8, C9, C16, C17, C18 are each independently a carbon atom, a silicon atom or other heteroatom, and at least one ring-forming atom is a silicon atom and constitutes a silicon hydroxyl group, and at least one ring-forming atom is attached to other atoms of the compound; the hydrogen atoms on the ring atoms of the cyclic structures in C7, C8, C9, C16, C17 and C18 can be substituted or unsubstituted; the cyclic structure in C7, C8, C9, C16, C17 and C18 can be a single ring structure, a multi-ring structure, a spiro ring structure, a condensed ring structure, a bridged ring structure and a nested ring structure; Indicating the connection to other elements of the compound.

Wherein the cyclic structure in C7, C8, C9, C16, C17, C18 may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: silacycloalkanes, cyclosiloxanes, cyclosilazanes, cyclosilathiolanes, cyclosilaphosphanes, cyclosilaboranes, silabenzenes, silanaphthalenes, silaxanthenes, silaphenanthrenes, silaarenes; the cyclic structures listed are preferably silacyclopentane, silacyclohexane, silacyclohexene, siladiene, silahexenone, silabenzene, cyclotrisiloxane, cyclotrisilazane, and cyclohexasilazane. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

the structure of the above-exemplified compound (IV) containing a silicon hydroxyl group/silicon hydroxyl group precursor is only presented for better explanation of typical structures that the compound (IV) containing a silicon hydroxyl group/silicon hydroxyl group precursor has under such conditions, and only representative structures under such conditions are presented, not limiting the scope of the present invention.

Wherein, when the compound (IV) of the silicon hydroxyl/silicon hydroxyl-containing precursor contains any one or more than two organic silicon structural motifs, the motifs can be connected with each other through a connecting group J, and the connecting group J can be selected from any one or more than one of the following: a single bond, a heteroatom linker, a divalent or multivalent small molecule hydrocarbyl radical having a molecular weight of no more than 1000Da, a divalent or multivalent polymer chain residue having a molecular weight of greater than 1000Da, a divalent or multivalent inorganic small molecule chain residue having a molecular weight of no more than 1000Da, a divalent or multivalent inorganic large molecule chain residue having a molecular weight of greater than 1000 Da;

When J is selected from a single bond, it may be selected from a silicon single bond, a carbon single bond, a carbon nitrogen single bond, a nitrogen single bond, a silicon carbon single bond, a silicon nitrogen single bond; j is preferably a silicon-silicon single bond, a carbon-carbon single bond, or a silicon-carbon single bond. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

When J is selected from a heteroatom linker, it may be selected from any one or a combination of any of the following: ether group, thio group, thioether group, divalent tertiary amine group, trivalent tertiary amine group, divalent silicon group, trivalent silicon group, tetravalent silicon group, divalent phosphorus group, trivalent phosphorus group, divalent boron group, trivalent boron group; j is preferably an ether group, a thio group, a divalent tertiary amine group, or a trivalent tertiary amine group. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

When J is selected from the group consisting of small divalent or multivalent hydrocarbon radicals of molecular weight not exceeding 1000Da, which generally contain 1 to 71 carbon atoms, the valence of the hydrocarbon radical may be 2 to 144, which may or may not contain a heteroatom group. In general terms, the divalent or multivalent small molecule hydrocarbyl group may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: two to one hundred forty-four valence C _1-71 Alkyl, two to one hundred forty-four valence rings C _3-71 Alkyl, di-to hexavalent phenyl, di-to octavalent benzyl, di-to one hundred forty-valent aromatic hydrocarbon groups; j is preferably a di-to tetravalent methyl group, a di-to hexavalent ethyl group, a di-to octavalent propyl group, a di-to hexavalent cyclopropane group, a di-to octavalent cyclobutyl group, a di-to decavalent cyclopentyl group, a di-to dodecavalent cyclohexyl group, or a di-to hexavalent phenyl group. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

wherein g and h are each independently a fixed value or an average value, and g is more than or equal to 20, and h is more than or equal to 20.

When J is selected from a divalent or multivalent polymer chain residue having a molecular weight greater than 1000Da, it may be any suitable divalent or multivalent polymer chain residue, including but not limited to a divalent or multivalent carbon chain polymer residue, a divalent or multivalent hetero chain polymer residue, a divalent or multivalent element organic polymer residue. Wherein, the polymer can be a homopolymer or a copolymer composed of any of several monomers, oligomers or polymers; the polymer chains may be flexible chains or rigid chains.

When J is selected from a divalent or multivalent carbon chain polymer residue, it may be any suitable polymer residue whose macromolecular backbone is composed primarily of carbon atoms, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybrid forms of any one: divalent or polyvalent polyolefin chain residues such as a divalent or polyvalent polyethylene chain residue, a divalent or polyvalent polypropylene chain residue, a divalent or polyvalent polyisobutylene chain residue, a divalent or polyvalent polystyrene chain residue, a divalent or polyvalent polyvinyl chloride chain residue, a divalent or polyvalent polyvinylidene chloride chain residue, a divalent or polyvalent polyvinyl fluoride chain residue, a divalent or polyvalent polytetrafluoroethylene chain residue, a divalent or polyvalent chlorotrifluoroethylene chain residue, a divalent or polyvalent polyvinyl alcohol chain residue, a divalent or polyvalent polyvinyl alkyl ether chain residue, a divalent or polyvalent polybutadiene chain residue, a divalent or polyvalent polyisoprene chain residue, a divalent or polyvalent polychloroprene chain residue, a divalent or polyvalent polynorbornene chain residue, and the like; divalent or polyvalent polyacrylic chain residues such as divalent or polyvalent polyacrylic chain residues, divalent or polyvalent polyacrylamide chain residues, divalent or polyvalent polymethyl acrylate chain residues, divalent or polyvalent polymethyl methacrylate chain residues, and the like; divalent or polyvalent polyacrylonitrile-based chain residues, such as divalent or polyvalent polyacrylonitrile-based chain residues, and the like. J is preferably a divalent or multivalent polyethylene chain residue, a divalent or multivalent polypropylene chain residue, a divalent or multivalent polystyrene chain residue, a divalent or multivalent polyvinyl chloride chain residue, a divalent or multivalent polybutadiene chain residue, a divalent or multivalent polyisoprene chain residue, a divalent or multivalent polyacrylic chain residue, a divalent or multivalent polyacrylamide chain residue, a divalent or multivalent polyacrylonitrile chain residue. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

When J is selected from a divalent or polyvalent heterochain polymer residue, it may be any suitable polymer residue whose macromolecular backbone is composed predominantly of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybridized forms of any one: divalent or polyvalent polyether chain residues such as divalent or polyvalent polyethylene oxide chain residues, divalent or polyvalent polypropylene oxide chain residues, divalent or polyvalent polytetrahydrofuran chain residues, divalent or polyvalent epoxy resin chain residues, divalent or polyvalent phenolic resin chain residues, divalent or polyvalent polyphenylene ether chain residues, etc.; divalent or multivalent polyester chain residues, such as divalent or multivalent polycaprolactone chain residues, divalent or multivalent polylactide chain residues, divalent or multivalent polyethylene terephthalate chain residues, divalent or multivalent unsaturated polyester chain residues, divalent or multivalent alkyd chain residues, divalent or multivalent polycarbonate chain residues, and the like; divalent or multivalent polyamine chain residues, such as divalent or multivalent polyamide chain residues, divalent or multivalent polyimide chain residues, divalent or multivalent polyurethane chain residues, divalent or multivalent polyurea chain residues, divalent or multivalent urea resin chain residues, divalent or multivalent melamine resin chain residues, etc. J is preferably a divalent or multivalent polyethylene oxide chain residue, a divalent or multivalent polytetrahydrofuran chain residue, a divalent or multivalent epoxy resin chain residue, a divalent or multivalent polycaprolactone chain residue, a divalent or multivalent polylactide chain residue, a divalent or multivalent polyamide chain residue. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

Wherein g, h, j, k is a fixed value or an average value independently, preferably g is not less than 36, h is not less than 36, j is not less than 12, and k is not less than 12.

When J is selected from a divalent or polyvalent element organic polymer residue, it may be any suitable polymer residue whose macromolecular backbone is composed primarily of inorganic element heteroatoms such as silicon, boron, aluminum, and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus, and the like, which may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybridized forms of any one: divalent or multivalent organosilicon-based polymer chain residues, such as divalent or multivalent polyorganosiloxane chain residues, divalent or multivalent polyorganosiloxane nitrogen chain residues, divalent or multivalent polyorganosiloxane sulfur chain residues, divalent or multivalent polyorganosiloxane chain residues; divalent or multivalent organoboron based polymer chain residues, such as divalent or multivalent polyorganoborane chain residues, divalent or multivalent polyorganoborazine chain residues, and the like; divalent or polyvalent organophosphorus polymer chain residues; divalent or polyvalent organolead based polymer chain residues; divalent or polyvalent organotin-based polymer chain residues; divalent or polyvalent organic arsenic-based polymer chain residues; divalent or polyvalent organic antimony-based polymer chain residues. J is preferably a divalent or polyvalent polyorganosiloxane chain residue, a divalent or polyvalent polyorganosiloxane chain residue. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

When J is selected from a divalent or multivalent inorganic small molecule chain residue having a molecular weight of not more than 1000Da, it may be any suitable inorganic small molecule chain residue having a molecular main chain and side chains both consisting essentially of inorganic element heteroatoms such as silicon, boron, aluminum, and the like, and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus, and the like, said divalent or multivalent inorganic small molecule chain residue may be selected from any one of the following groups, unsaturated forms of any one, substituted forms of any one, or hybridized forms of any one: a divalent or multivalent silane chain residue, a divalent or multivalent silicon compound chain residue, a divalent or multivalent sulfur nitrogen compound chain residue, a divalent or multivalent phosphazene compound chain residue, a divalent or multivalent phosphorus oxide compound chain residue, a divalent or multivalent borane chain residue, a divalent or multivalent boron oxide compound chain residue. J is preferably a divalent or polyvalent silane chain residue, a divalent or polyvalent siloxane chain residue, a divalent or polyvalent phosphazene chain residue, a divalent or polyvalent borane chain residue. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

When J is selected from divalent or polyvalent inorganic macromolecular chain residues having a molecular weight of greater than 1000Da, it may be any suitable inorganic macromolecular chain residue in which the main chain and side chain of the macromolecule are composed mainly of heteroatoms of inorganic elements such as silicon, boron, aluminum and the like and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and the like.

Wherein J may be selected from any one of the following groups, an unsaturated form of any one, a substituted form of any one, or a hybridized form of any one: divalent or multivalent polysilane chain residues, divalent or multivalent polysiloxane chain residues, divalent or multivalent polysulfide silicon chain residues, divalent or multivalent polysulfide nitrogen chain residues, divalent or multivalent polyphosphate chain residues, divalent or multivalent polyphosphazene chain residues, divalent or multivalent polychlorophosphazene chain residues, divalent or multivalent polyborophosphazene chain residues, divalent or multivalent polyborone chain residues. J is preferably a divalent or polyvalent polysilane chain residue, a divalent or polyvalent polysiloxane chain residue, a divalent or polyvalent polyphosphazene chain residue, a divalent or polyvalent polyborane chain residue. Suitable silicon hydroxyl/silicon hydroxyl precursor containing compound (IV) structures formed are exemplified as follows:

Wherein g, h and i are each independently a fixed value or an average value, preferably g is more than or equal to 36, h is more than or equal to 36, and i is more than or equal to 36.

J may also be selected from any one of the following groups of residue-bearing inorganic macromolecules or any one of the surface-modified residue-bearing inorganic macromolecules: zeolite molecular sieves, aluminum phosphate molecular sieves, zirconium phosphate molecular sieves, heteropolyacid salt molecular sieves, diamond, graphite, graphene oxide, carbon nanotubes, fullerenes, carbon fibers, white phosphorus, red phosphorus, phosphorus pentoxide, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talc, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramic, boron oxide, sulfur nitride, calcium silicide, silicate, glass fibers, beryllium oxide, magnesium oxide, mercury oxide, borohydride, boron nitride, boron carbide, aluminum nitride, diaspore, gibbsite, corundum, titanium dioxide. J is preferably surface modified graphene, surface modified carbon fiber, surface modified silica, surface modified silicon nitride, surface modified silicon carbide, surface modified silicate, surface modified glass fiber, surface modified boron nitride. Suitable compounds (IV) containing silicon hydroxyl groups/silicon hydroxyl groups precursors formed are generally inorganic structures, such as, for example: silicon nitride with silicon hydroxyl on the surface, silicon carbide with silicon hydroxyl on the surface, silicon dioxide with silicon hydroxyl on the surface, silicate with silicon hydroxyl on the surface, and glass fiber with silicon hydroxyl on the surface.

In embodiments of the present invention, one compound may also contain at least two of a dihydroxy moiety, a monohydroxy moiety, and a silanol/silanol precursor simultaneously, i.e., a dihydroxy moiety and a monohydroxy moiety simultaneously, a dihydroxy moiety and a silanol/silanol precursor simultaneously, a monohydroxy moiety and a silanol/silanol precursor simultaneously, a dihydroxy moiety, a monohydroxy moiety, and a silanol/silanol precursor simultaneously. Such compounds may be classified into any of the compounds (II), (III) and (IV), and the specific structures thereof will not be described herein.

In the embodiment of the invention, the compound (V) simultaneously contains at least one of various hydroxyl groups and an organoboric acid group, wherein the selection method of the organoboric acid group can refer to the definition of the organoboric acid group in the organoboron compound (I), and the description thereof is omitted herein; the various hydroxyl moieties may be selected from dihydroxy moieties, monohydroxy moieties, silylhydroxy/silylhydroxy precursors. The compound formed may be selected from: a compound containing both an organoboronic acid moiety and a dihydroxy moiety, a compound containing both an organoboronic acid moiety and a monohydroxy moiety, a compound containing both an organoboronic acid moiety and a dihydroxy/silanol precursor, a compound containing both an organoboronic acid moiety and a dihydroxy moiety and a monohydroxy/silanol precursor, a compound containing both an organoboronic acid moiety and a dihydroxy moiety and a silanol/silanol precursor, a compound containing both an organoboronic acid moiety and a monohydroxy/silanol precursor, and a compound containing both an organoboronic acid moiety and a dihydroxy moiety and a monohydroxy/silanol precursor. The specific structure is not exemplified again and a person skilled in the art can make a reasonable choice according to the logic and context of the present invention.

In the embodiment of the present invention, the compound (VI) containing a dynamic covalent bond and other reactive groups, wherein the dynamic covalent bond is selected from the group consisting of an organoboronate cyclic ester bond, an organoboronate monoester bond, an organoboronate silicon ester bond and an organoboronate anhydride bond, and the specific selection method thereof may refer to the definition of various dynamic covalent bonds and is not described herein again; the other reactive group may be one or more.

In the embodiment of the present invention, the compound (VII) containing no organoboronic acid moiety, various hydroxy moieties and organoboronic acid ester bond but containing other reactive groups is not particularly limited in its structure, and any suitable compound containing no organoboronic acid group, organoboronic acid ester group, various hydroxy moieties and organoboronic acid ester bond but containing other reactive groups may be selected as the compound (VII) in the present invention.

The present invention provides a method for preparing a dynamic polymer based on a combined dynamic covalent bond, the dynamic polymer having a linear or cyclic structure, which is preferably prepared by at least one of the following means (but the present invention is not limited thereto):

first, it is obtained by the reaction of at least the following components in the reaction to form a dynamic covalent bond: at least one organoboron compound (I), at least two hydroxyl-containing compounds selected from the group consisting of organoboron group-containing compound I and/or compound II and/or compound III and/or compound (IV), the same applies below; wherein the organoboron compound (I) and the hydroxyl-containing compound each contain at most two functional groups;

first, it is obtained by the reaction of at least the following components in the reaction to form a dynamic covalent bond: at least one organoboron compound (I), at least two hydroxyl-containing compounds (selected from the group consisting of compounds (II) to (IV), the same as described below); wherein at least one of the organoboron compound (I), the hydroxyl-containing compound contains at least three functional groups, and the combination thereof does not result in ordinary covalent crosslinking above the gel point;

third, it is obtained by the reaction of at least the following components in the reaction to form dynamic covalent bonds and ordinary covalent bonds: at least one compound (V), at least one compound (VII), or both, with at least one organoboron compound (I) or at least two hydroxyl-containing compounds or at least one organoboron compound (I) and at least two hydroxyl-containing compounds; wherein the compound (V), the organoboron compound (I), the hydroxyl-containing compound each contain up to two functional groups and at least one compound (V) or organoboron compound (I) or hydroxyl-containing compound contains at least one other reactive group and combinations thereof do not result in ordinary covalent crosslinking above the gel point.

The dynamic polymers used in the present invention for preparing the combined dynamic covalent bonds are not limited to being prepared using the several embodiments described above, but may be the several embodiments described above or a combination thereof with other embodiments. It is contemplated that the use of organoboron compounds (I), hydroxyl-containing compounds (II) - (IV), compounds (V), and compounds (VI) as starting materials in the embodiments herein, whether in the form of starting materials, as compounds synthesized from starting materials, or as intermediates for the synthesis of polymers, is intended to be within the scope of the present invention as it is contemplated by the teachings of the present invention. Likewise, the dynamic polymers described can be obtained by the person skilled in the art, with the aid of the teachings of the present invention, with reasonable implementation of the several compounds described above.

The dynamic polymer at least contains two types of dynamic covalent organic borate bonds, and the strength, the structure, the dynamic property, the responsiveness, the formation conditions and the like of the dynamic covalent organic borate bonds of different types are different, so that the synergistic and orthogonal performance effects can be achieved; moreover, the organic boric acid ester bonds can be mutually exchanged and converted under certain conditions, so that the structure and the performance of the material are more adjustable. The dynamic reactivity of the organic boric acid ester bond in the dynamic polymer is strong, and the dynamic reaction condition is mild. Compared with other existing dynamic covalent systems, the invention fully utilizes the good thermal stability and high dynamic reversibility of the organic borate bond, can realize the synthesis and dynamic reversibility of the dynamic polymer under the conditions of no need of catalyst, high temperature, illumination or specific pH, improves the preparation efficiency, reduces the limitation of the use environment and expands the application range of the polymer. In addition, by selectively controlling other conditions (e.g., adding adjuvants, adjusting reaction temperature, etc.), the dynamic covalent chemical equilibrium can be accelerated or quenched in a desired state under appropriate circumstances.

The ether ring mentioned in the present invention may be any ring containing an ether bond, and the ring-forming atoms are each independently a carbon atom, an oxygen atom or a heteroatom; the hetero atom may be selected from nitrogen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the ring-forming atom of the ether ring may be substituted with any substituent or may be unsubstituted; it may be a monocyclic structure, a polycyclic structure, a spiro structure, a condensed ring structure, a bridged ring structure, or a nested ring structure. In general terms, the ether ring includes, but is not limited to, ethylene oxide, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, furan, crown ether, and the like; the ether ring is preferably ethylene oxide or tetrahydrofuran.

The condensed ring mentioned in the present invention may be any ring containing a chemical bond formed by condensation of an amide bond, an ester bond, an imide, an acid anhydride, or the like, and each ring-forming atom is independently a carbon atom or a heteroatom; the hetero atom may be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the ring-forming atom of the condensed ring may be substituted with any substituent or may be unsubstituted; it may be a monocyclic structure, a polycyclic structure, a spiro structure, a condensed ring structure, a bridged ring structure, or a nested ring structure. In general terms, the condensed ring includes, but is not limited to, lactones, lactides, lactams, cyclic imides, cyclic anhydrides, cyclic peptides, and the like; the condensed ring is preferably caprolactone, lactide or caprolactam.

The term "molecular weight" as used herein refers to the relative molecular mass of a substance, and for small molecular compounds, small molecular groups, and certain macromolecular compounds, macromolecular groups having a fixed structure, the molecular weight is generally monodisperse, i.e., has a fixed molecular weight; in the case of oligomers, polymers, oligomer residues, polymer residues, and the like having a polydispersity molecular weight, the molecular weight generally refers to the average molecular weight. Wherein, the small molecular compound and the small molecular group in the invention refer to a compound or a group with the molecular weight not more than 1000 Da; macromolecular compounds, macromolecular groups refer in particular to compounds or groups having a molecular weight of greater than 1000 Da.

The term "organic group" as used herein refers to a group mainly composed of a carbon element and a hydrogen element as a skeleton, and may be a small molecular group having a molecular weight of not more than 1000Da or a residue of a polymer chain having a molecular weight of more than 1000Da, and examples of suitable groups include: methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde, acetyl, acetonyl, and the like.

The term "organosilicon group" as used herein refers to a group mainly composed of a silicon element and a hydrogen element as a skeleton, and may be a small molecular silane group having a molecular weight of not more than 1000Da or an organosilicon polymer chain residue having a molecular weight of more than 1000Da, and examples of suitable groups include: silane groups, siloxane groups, silasulfanyl groups, silazane groups, and the like.

The term "heteroatom" as used herein refers to a common non-carbon atom such as nitrogen, oxygen, sulfur, phosphorus, silicon, boron, and the like.

In the present invention, compounds in which a carbon atom at any position in a hydrocarbon is substituted with a heteroatom are collectively referred to as "hetero hydrocarbons".

The term "alkyl" as used herein refers to a saturated hydrocarbon group having a straight or branched chain structure. Where appropriate, the alkyl groups may have the indicated number of carbon atoms, e.g. C _1-4 Alkyl groups, including alkyl groups having 1, 2, 3 or 4 carbon atoms in a straight or branched chain arrangement. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl, decyl.

The term "cycloalkyl" as used herein refers to saturated cyclic hydrocarbons. Cycloalkyl rings can include the indicated number of carbon atoms. For example, a 3 to 8 membered cycloalkyl group includes 3, 4, 5, 6, 7, or 8 carbon atoms. Examples of suitable cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

The term "arene" as used in the present invention means any stable mono-or polycyclic carbocycle of up to 7 atoms in each ring, wherein at least one ring is aromatic. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, binaphthyl, tetrahydronaphthyl, indanyl, anthracyl, bianthracenyl, phenanthryl, biphenanthryl.

The term "heteroaralkyl" as used herein means a stable single or multiple ring of up to 7 atoms in each ring, wherein at least one ring is aromatic and at least one ring contains a heteroatom selected from O, N, S, P, si, B and the like. Heteroarenes within the scope of this definition include, but are not limited to, acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, quinazolinyl, pyrazolyl, indolyl, benzotriazole, furanyl, thienyl, thiophenyl, 3, 4-propylenedioxythiophenyl, benzothienyl, benzofuranyl, benzodioxan, benzodioxine, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, tetrahydroquinolinyl, thiazolyl, isothiazolyl, 1,2, 4-triazolyl, 1,2, 3-triazolyl, 1,2, 4-oxadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2,4, 5-tetrazinyl and tetrazolyl.

For simplicity, the range of carbon atoms in the group is also marked in the subscript position of C in the present invention to denote the number of carbon atoms the group has, e.g., C _1-10 Represents a compound having 1 to 10 carbon atoms, C _3-20 Representing a compound having 3 to 20 carbon atoms. "unsaturated C _3-20 Hydrocarbon "means C _3-20 A compound having an unsaturated bond in a hydrocarbon group. "substituted C _3-20 Hydrocarbon "means C _3-20 A compound in which a hydrogen atom of a hydrocarbon group is substituted. "hybrid C _3-20 Hydrocarbon "means C _3-20 A compound obtained by substituting a heteroatom for a carbon atom in a hydrocarbon group. When a group is selected from C _1-10 When the hydrocarbon group is selected from any hydrocarbon group having carbon atoms in the range indicated by the subscript, it may be selected from C ₁ 、C ₂ 、C ₃ 、C ₄ 、C ₅ 、C ₆ 、C ₇ 、C ₈ 、C ₉ 、C ₁₀ Any one of the hydrocarbon groups. In the present invention, unless otherwise specified, subscripts labeled in the form of intervals each represent any integer which may be selected from the range, including both endpoints.

For simplicity, a class of symbol designations of similar meaning having consecutive serial numbers are also linked in the present invention by the term "to" which means that the designation linked by the term "to" includes each symbol designation between the serial number intervals, e.g., the group R ₁ ～R ₃ Represented by the radical R ₁ Radicals R ₂ Radicals R ₃ The method comprises the steps of carrying out a first treatment on the surface of the For another example, B1 to B4 are B1, B2, B3 and B4. The symbols "-" appearing elsewhere in the present invention all represent such meanings.

When the structure referred to in the present invention has an isomer, any of the isomers may be used without particular designation, and include positional isomerism, conformational isomerism, chiral isomerism, cis-trans isomerism and the like.

The positional isomerism described in the present invention includes positional isomerism due to the difference in the position of substituents, functional groups or linking groups on dihydroxy moieties or organoboronic acid moieties.

In the present invention, "substituted" is exemplified by "substituted hydrocarbon group" and means that any one or more hydrogen atoms at any position in the substituted "hydrocarbon group" may be substituted with any substituent. In the case where there is no particular limitation, the substituent is not particularly limited.

For a compound, a group or an atom, it is possible to simultaneously be substituted and hybridized, for example nitrophenyl for the hydrogen atom, for example, -CH ₂ -CH ₂ -CH ₂ -replaced by-CH ₂ -S-CH(CH ₃ )-。

For simplicity of explanation, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the conjunction "and/or" previously described options, or from the conjunction "and/or" subsequently described options, or from the conjunction "and/or" previously and subsequently described options.

The compounds (I) to (VII) used for preparing the dynamic polymers may be gases, liquids, crystals, powders, granules, gels, pastes, etc.

In the preparation of the dynamic polymer, when the organic boric acid unit in the organic boron compound (I) exists in the form of organic boric acid ester, organic borate and organic haloborane, the organic boric acid unit can be firstly hydrolyzed to form organic boric acid in the process of reacting with the hydroxyl group-containing compound (containing organic boric acid group) and/or compound (II) and/or compound (III) and/or compound (IV)) and then react with the hydroxyl group unit in the hydroxyl group-containing compound (containing organic boric acid group) and/or compound (II) and/or compound (III) and/or compound (IV)) to form the dynamic covalent bond; when the organoboron moiety in the organoboron compound (I) is present as an organoborate ester, a novel dynamic covalent bond can be formed by directly reacting the organoboron moiety in the compound (I and/or II and/or III and/or IV) and the hydroxyl moiety in the compound (V) through transesterification.

For the compound (V) containing at least two of various hydroxyl moieties and organoboronic acid moieties at the same time, it is generally necessary to control the reaction conditions and add a suitable reaction auxiliary agent so that the hydroxyl moieties in the compound (V) can react with the organoboronic acid moieties contained in the same or different compounds (V) to form the dynamic covalent bond only during the polymer preparation process, thereby obtaining the dynamic polymer. In one polymerization system, one or more organoboron compounds (I) and/or one or more hydroxyl-containing compounds (organoboron-containing compound I and/or compound II and/or compound III and/or compound IV) may be contained in addition to one or more compounds (V). When the starting material is selected from the group consisting of the compound (V), the organoboronic acid moiety in the compound (V) is preferably present in the form of an organoboronate ester in order to ensure the stability of the starting material. In view of the relatively complicated preparation and storage processes of the compound (V), the raw material components for preparing the dynamic polymer are preferably selected from organoboron compounds (I) and hydroxyl-containing compounds (organoboron group-containing compounds I and/or II and/or III and/or IV).

In an embodiment of the present invention, the organoboron compound (I), the hydroxyl-containing compounds (IIII) to (IV) and the compound (V) are reacted in the course of forming the dynamic monomer and/or prepolymer and/or polymer by using the hydroxyl group and/or organoboric acid group contained in the compound, and optionally other components such as the compound (VI) and/or the compound (VII) by using other reactive groups contained in the compound at the same time, through a common covalent linkage by polymerization reaction, to constitute the dynamic polymer. It is also possible to blend the organoboron compounds (I), hydroxyl-containing compounds (II) to (IV), compounds (V) and/or polymers which participate in the formation of prepolymers and/or polymers with other components, such as compounds (VI) and/or compounds (VII), and then to form dynamic polymers by ordinary covalent attachment of the other components. Or the common covalent linkage can be formed first, and then the dynamic organic borate ester bond can be formed.

The compound (VI) is generally a dynamic polymer containing dynamic covalent bonds obtained by an interaction between other reactive groups contained in the compound (VI) or by an interaction between other reactive groups contained in the compound (VI) and other reactive groups contained in the compound (VII) and/or the prepolymer and/or polymer formed by the organoboron compound (I), the hydroxyl-containing compounds (II) to (IV) and the compound (V). The general covalent linkage can also be formed directly from the reaction of other reactive groups contained in the compound (VI) itself. Of course, the present invention is not limited thereto and those skilled in the art can implement the logic and context of the present invention reasonably efficiently.

In embodiments of the invention, other reactive groups may be reacted to give a common covalent bond by, for example, the following forms of reactions, thereby forming a dynamic polymer with the organoboronic acid ester linkage: an amide bond is formed by a condensation reaction between an amino group contained in the compound and a carboxyl group contained in the compound; the epoxy group contained in the compound and amino and sulfhydryl contained in the compound undergo a ring-opening reaction to form a secondary amine bond and a thioether bond; free radical polymerization is carried out through olefin groups contained in the compound under the action of an initiator or external energy; under the action of an initiator or external energy, carrying out anionic/cationic polymerization through olefin groups contained in the compound; forming urea bonds, urethane bonds and thiocarbamate bonds by reacting isocyanate groups contained in the compound with amino groups, hydroxyl groups and mercapto groups contained in the compound; ring-opening polymerization is carried out through epoxy groups contained in the compound to form ether bonds; under the catalysis of monovalent copper, cuAAC reaction is carried out through azide groups contained in the compound and alkynyl groups contained in the compound; performing a thio-ene click reaction through a mercapto group contained in the compound and an olefin group contained in the compound; by addition reaction between double bonds contained in the compound, or the like; among them, a means capable of rapidly reacting at not higher than 100 ℃ is preferable, and a means capable of rapidly reacting at room temperature is more preferable, including but not limited to a reaction of an isocyanate group with an amino group, a hydroxyl group, a mercapto group, an acrylate reaction, a thio-ene click reaction.

Suitable polymerization methods mentioned in embodiments of the present invention, which may be carried out by any suitable polymerization reaction commonly used in the art, include, but are not limited to, condensation polymerization, addition polymerization, ring-opening polymerization; among them, addition polymerization includes, but is not limited to, radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization.

In particular embodiments, the compound starting material may be carried out by any suitable polymerization process commonly used in the art, using any of the polymerization methods described above. For example, when the compound starting material is a dynamic polymer obtained in the form of condensation polymerization, it may be carried out by a polymerization process such as melt polymerization, solution polymerization, interfacial polymerization, or the like; for another example, when the compound starting material is a dynamic polymer obtained in the form of radical polymerization, it may be carried out by a polymerization process such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like; for another example, when the compound starting material is a dynamic polymer obtained in the form of ionic polymerization, it may be carried out by a polymerization process such as solution polymerization, slurry polymerization, gas phase polymerization, or the like.

In the preparation process, a solution polymerization process or an emulsion polymerization process is preferably used to prepare the dynamic polymer. The solution polymerization process and the emulsion polymerization process have the advantages of being capable of reducing the viscosity of a system, easy to transfer mass and heat, convenient to control the temperature and capable of avoiding local overheating, and the obtained solution and emulsion are convenient to concentrate or disperse and are favorable for carrying out operations such as coating, mixing and the like.

In the present invention, the organic boric acid moiety constituting the organic boric acid ester bond of the dynamic polymer is easily attacked by the nucleophile containing an unshared electron pair to generate bonding due to electron deficiency of the boron atom; in addition, various hydroxyl-containing moieties constituting the organoboronic acid ester bond have an unshared electron pair in the oxygen atom, and thus, in the course of contact with the organoboronic acid moiety, the organoboronic acid ester bond can be formed by a reaction such as a dehydration condensation reaction or a transesterification reaction, thereby constituting a dynamic polymer. The invention utilizes the dynamic reversibility of organic boric acid ester bonds to prepare the dynamic polymer.

In embodiments of the present invention, the dynamic polymer or composition thereof may be in the form of a solution, emulsion, paste, gel, normal solid, elastomer, gel (including hydrogel, organogel, oligomer-swollen gel, plasticizer-swollen gel, ionic liquid-swollen gel), foam, etc., wherein the normal solid and foam generally contain no more than 10wt% of soluble small molecular weight components, and the gel generally contains no less than 50wt% of small molecular weight components. The dynamic polymer common solid has the advantages of fixed shape and volume, high strength and high density, is suitable for high-strength explosion-proof walls or instrument shells, and has good self-repairing property and recoverability; the elastic body has the characteristics of elasticity and damping/energy absorption, is softer, and has higher self-repairing property; the dynamic polymer gel is soft in texture, has better energy absorption and elasticity, is suitable for preparing high-damping energy absorption materials, and has good self-repairing property and recoverability; when the dynamic polymer foam material has the advantages of low density, portability, high specific strength and the like of general foam plastics, the soft foam material also has good elasticity and energy absorption, and in addition, the dynamic polymer foam material also has good self-repairing property and recycling property.

In an embodiment of the present invention, the dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof), or may be obtained by swelling with a swelling agent after the completion of the preparation of the dynamic polymer. Of course, the present invention is not limited thereto and those skilled in the art can implement the logic and context of the present invention reasonably efficiently.

In the preparation process of the dynamic polymer, three methods of 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 to introduce a large amount of air or other gases into emulsion, suspension or solution of the polymer by means of strong stirring in the preparation process of the dynamic polymer to form a uniform foam, and then to gel and solidify the foam by physical or chemical change to form the foam material. Air may be introduced and emulsifiers or surfactants may be added to shorten the molding cycle.

The physical foaming method realizes the foaming of the polymer by utilizing a physical principle in the preparation process of the dynamic polymer, and generally comprises the following four methods: (1) Inert gas foaming, namely, pressing inert gas into molten polymer or pasty material under the condition of pressurization, and then decompressing and heating to expand and foam the dissolved gas; (2) Evaporating, gasifying and foaming by utilizing low-boiling point liquid, namely pressing the low-boiling point liquid into a polymer or dissolving the liquid into polymer particles under certain pressure and temperature conditions, and then heating and softening the polymer, so that the liquid is evaporated, gasified and foamed; (3) The dissolution method is to immerse the polymer with liquid medium to dissolve the solid matter added in advance, so that a large amount of pores appear in the polymer to form foaming, for example, the soluble matter salt is firstly mixed with the polymer, after the product is formed, the product is put in water for repeated treatment, and the soluble matter is dissolved out to obtain the open-cell foam product; (4) Hollow microsphere method, namely adding hollow microspheres into plastic and curing to form closed cell foam plastic; among them, foaming is preferably carried out by a method of dissolving an inert gas and a low boiling point liquid in a polymer. The physical foaming method has the advantages of low toxicity in operation, low foaming raw material cost, no residual foaming agent and the like. In addition, the preparation can also be carried out by a freeze-drying method.

Wherein, the chemical foaming method is a foaming method which generates gas along with chemical reaction in the foaming process of dynamic polymer, and generally comprises the following two methods: (1) The thermal decomposition type foaming agent foaming method is to foam the gas decomposed and released after heating by using a chemical foaming agent. (2) Foaming processes in which interactions between polymer components produce a gas, i.e., the foaming process in which a chemical reaction between two or more components in a foaming system is used to produce an inert gas (e.g., carbon dioxide or nitrogen) to expand the polymer. In the foaming process, in order to control the balance of polymerization reaction and foaming reaction, a small amount of catalyst and foam stabilizer (or surfactant) are generally added to ensure good quality of the product. Among them, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

In the preparation process of the dynamic polymer, three methods of compression molding foaming molding, injection foaming molding and extrusion foaming molding are mainly adopted to mold the dynamic polymer foam material.

The compression molding foaming molding process is simple and easy to control, and can be divided into a one-step method and a two-step method. The one-step molding refers to that the mixed materials are directly put into a mold cavity for foam molding; the two-step method is to pre-foam the mixed materials, and then put the materials into a die cavity for foam molding. Among them, the one-step method is preferable because the one-step method is more convenient to operate and has higher production efficiency than the two-step method.

The process and the equipment are similar to those of the common injection molding, the material is heated and rubbed to be in a melt state after being added into a screw in the bubble nucleation stage, the foaming agent is injected into the melt of the material through a control valve of a metering valve at a certain flow rate, and then the foaming agent is uniformly mixed through a mixing element at the head of the screw, so that bubble nuclei are formed under the action of the nucleating agent. The expansion stage and the solidification and shaping stage are both carried out after the mold cavity is filled, when the pressure of the mold cavity is reduced, the expansion process of bubble nuclei occurs, and simultaneously, the bubble body is solidified and shaped along with the cooling of the mold.

The extrusion foaming molding process and equipment are similar to those of the common extrusion molding, the foaming agent is added into an extruder before or during extrusion, the pressure of a melt flowing through a machine head is reduced, and the foaming agent volatilizes to form a required foaming structure. The foam molding technology is the most widely used foam molding technology at present, because the foam molding technology not only can realize continuous production, but also is more competitive in cost than injection foam molding.

In the preparation of the dynamic polymer, a person skilled in the art can select a proper foaming method and a foam molding method according to the actual preparation condition and the performance of the target polymer to prepare the dynamic polymer foam.

In an embodiment of the present invention, the structure of the dynamic polymer foam material relates to three of an open cell structure, a closed cell structure, and a half-open and half-closed structure. In the open pore structure, the cells are mutually communicated or completely communicated, and the single dimension or three dimensions can pass through gas or liquid, and the pore diameter of the cells is 0.01-3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from the cells by wall membranes, most of the cells are not mutually communicated, and the pore diameters of the cells are 0.01-3 mm. The contained foam holes are of semi-open structures with structures which are not communicated with each other. For the foam structure which has formed closed cells, it can also be made into an open cell structure by mechanical pressure or chemical method, and the person skilled in the art can choose according to the actual need.

In embodiments of the present invention, dynamic polymer foams are classified by their hardness into three categories, soft, hard and semi-hard: (1) A flexible foam having an elastic modulus of less than 70MPa at 23 ℃ and 50% relative humidity; (2) Rigid foam having an elastic modulus greater than 700MPa at 23 ℃ and 50% relative humidity; (3) Semi-rigid (or semi-flexible) foams, foams between the two classes, have an elastic modulus between 70MPa and 700 MPa.

In embodiments of the present invention, dynamic polymer foams can be further classified into low foaming, medium foaming and high foaming according to their density. Low foaming foam material having a density greater than 0.4g/cm ³ The foaming multiplying power is less than 1.5; a density of 0.1 to 0.4g/cm ³ The foaming multiplying power is 1.5-9; while the high foaming foam material has a density of less than 0.1g/cm ³ The foaming ratio is more than 9.

In the preparation process of the dynamic polymer, certain additive and filler can be added to jointly form the dynamic polymer material, but the additives are not required.

In the preparation process of the dynamic polymer material, certain additives which can be added 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 additive can be any one or more of the following additives: synthesis aids including catalysts, initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; auxiliaries for improving mechanical properties, including toughening agents; auxiliary agents for improving processability, including lubricants and release agents; the softening and light auxiliary agent comprises a plasticizer, a foaming agent and a dynamic regulator; adjuvants for modifying surface properties, including antistatic agents, emulsifiers, dispersants; auxiliary agents for changing the color light, including colorants, fluorescent whitening agents, matting agents; flame retardant and smoke suppressant additives, including flame retardants; other auxiliary agents, including nucleating agents, rheology agents, thickeners, leveling agents.

The catalyst in the additive can accelerate the reaction rate of reactants in the reaction process by changing the reaction path and reducing the reaction activation energy. Including but not limited to any ofOne or any of several catalysts: (1) catalyst for polyurethane synthesis: amine catalysts such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, tetramethyldipropylene triamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylene diamine, N, N, N ', N ', N ' -pentamethyldiethylene triamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropyl hexanoic acid, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, and the like; organometallic catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctanoate, lead isooctanoate, potassium oleate, zinc naphthenate, cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, and the like; (2) catalyst for polyolefin synthesis: such as Ziegler-Natta catalysts, pi-allyl nickel, alkyl lithium catalysts, metallocene catalysts, diethyl aluminum monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride diethyl ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, sesquiethyl aluminum chloride, vanadium oxychloride, triisobutyl aluminum, nickel naphthenate, rare earth naphthenate, and the like; (3) CuAAC reaction catalyst: synergistic catalysis is shared by monovalent copper compounds and amine ligands; the monovalent copper compound may be selected from Cu (I) salts, such as CuCl, cuBr, cuI, cuCN, cuOAc, etc.; or Cu (I) complexes, e.g. [ Cu (CH) ₃ CN) ₄ ]PF ₆ 、[Cu(CH ₃ CN) ₄ ]OTf、CuBr(PPh ₃ ) ₃ Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium hydrophosphate, etc.; (4) thio-ene reaction catalyst: photocatalysts such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2-dimethoxy-2-phenylacetophenone, and the like; nucleophilic reagent catalysts such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine, and the like. Used in the processThe amount of the catalyst is not particularly limited, but is generally 0.01 to 0.5wt%.

The initiator in the additive can cause the activation of monomer molecules to generate free radicals in the polymerization reaction process, improve the reaction rate and promote the reaction, and comprises any one or any several initiators including but not limited to the following: (1) initiator for radical polymerization: organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylpivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; (2) initiator for living polymerization: such as 2, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine ternary system, etc.; (3) initiator for ionic polymerization: such as butyllithium, sodium/naphthalene systems, boron trifluoride/water systems, tin tetrachloride/haloalkane systems, and the like; (4) initiator for coordination polymerization: such as titanium tetrachloride/triethylaluminum systems, dichlorozirconocene/methylaluminoxane systems, etc.; (5) initiator for ring-opening polymerization: such as sodium methoxide, potassium methoxide, ethylenediamine, 1, 6-hexamethylene diisocyanate, stannous octoate, and the like. Among them, preferred are lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile and potassium persulfate. The amount of the initiator used is not particularly limited, but is generally 0.1 to 1% by weight.

The antioxidant in the additive can delay the oxidation process of the polymer material, ensure that the material can be processed smoothly and prolong the service life of the material, and comprises any one or more antioxidants as follows: hindered phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-tert-butylphenol); sulfur-containing hindered phenols such as 4,4 '-thiobis- [ 3-methyl-6-t-butylphenol ], 2' -thiobis- [ 4-methyl-6-t-butylphenol ]; triazine-based hindered phenols such as 1,3, 5-bis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] -hexahydro s-triazine; blocked phenols of the trimeric isocyanate type, such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate; amines such as N, N ' -di (β -naphthyl) p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine; sulfur-containing compounds such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphites, such as triphenyl phosphite, trisnonylphenyl phosphite, tris [2, 4-di-tert-butylphenyl ] phosphite, etc., wherein the antioxidants are preferably Tea Polyphenol (TP), butyl Hydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010). The amount of the antioxidant used is not particularly limited, but is generally 0.01 to 1wt%.

The light stabilizer in the additive can prevent the polymer material from photo-aging and prolong the service life of the polymer material, and comprises any one or any several light stabilizers as follows: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, and calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-cyano-3, 3-diphenylacrylic acid 2-ethylhexyl ester; precursor ultraviolet absorbers such as p-tert-butylphenyl salicylate, bisphenol A bis-salicylate; ultraviolet quenchers such as monoethyl bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonate), 2' -thiobis (4-tert-octylphenoloxy) nickel; a hindered amine light stabilizer is used in the preparation of a light stabilizer, such as bis (2, 6-tetramethylpiperidine) sebacate, 2, 6-tetramethylpiperidine benzoate tris (1, 2, 6-pentamethylpiperidinyl) phosphite; other light stabilizers such as (2, 4-di-t-butylphenyl) 3, 5-di-t-butyl-4-hydroxybenzoate, alkylphosphamide, zinc N, N '-di-N-butyldithiocarbamate, nickel N, N' -di-N-Ding Zhengji dithiocarbamate, etc. Among them, carbon black and bis (2, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable, and the amount of the light stabilizer to be used is not particularly limited, but is generally 0.01 to 0.5wt%.

The heat stabilizer in the additive can prevent the polymer material from being chemically changed due to heating in the processing or using process or delay the changes to achieve the purpose of prolonging the service life, and comprises any one or any several of the following heat stabilizers but not limited to: lead salts such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, and zinc stearate; organotin compounds such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di-n-butyltin maleate, di-n-octyltin mono-n-octyltin dimaleate, isooctyl di-n-octyltin dimercaptoacetate, genins-C-102, isooctyl dimercaptoacetate, dimethyl tin dithiol and their complexes; antimony stabilizers, such as antimony mercaptides, antimony carboxylates; epoxy compounds such as epoxidized oils, epoxidized fatty acid esters, and epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triaryl alkyl phosphites, alkylaryl mixed esters, polymeric phosphites; polyols such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; composite heat stabilizers such as coprecipitated metal soaps, liquid metal soap composite stabilizers, organotin composite stabilizers, and the like. Among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di-n-butyltin maleate are preferable, and the amount of the heat stabilizer used is not particularly limited, and is generally 0.1 to 0.5wt%.

The toughening agent in the additive can reduce brittleness of the polymer material, increase toughness and improve material bearing strength, and comprises any one or any several of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-diene-copolymer, butadiene-styrene copolymer, and the like. Among them, the toughening agent is preferably ethylene propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS), chlorinated polyethylene resin (CPE), and the amount of the toughening agent used is not particularly limited, and is generally 5 to 10wt%.

The lubricant in the additive can improve the lubricity of the material, reduce friction and reduce interfacial adhesion, and comprises any one or any several of the following lubricants: saturated hydrocarbons and halogenated hydrocarbons such as paraffin wax, microcrystalline wax, liquid paraffin wax, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids, such as stearic acid; fatty acid esters such as fatty acid lower alcohol esters, fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides such as stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylenebisstearamide; fatty alcohols and polyols, such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, and the like. Among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, low molecular weight polyethylene, and the amount of the lubricant used is not particularly limited, and is generally 0.5 to 1wt%.

The release agent in the additive can make the polymer sample easy to release from the mold, has smooth and clean surface, and comprises any one or any several of the following release agents: paraffin, soaps, simethicone, ethyl silicone oil, methyl phenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicone rubber, polyvinyl alcohol and the like. Among them, the release agent is preferably simethicone, and the amount of the release agent used is not particularly limited, but is generally 0.5 to 2wt%.

The plasticizer in the additive can increase the plasticity of the polymer material, so that the hardness, modulus, softening temperature and embrittlement temperature of the polymer are reduced, and the elongation and the flexibility are improvedIncreased flexibility and flexibility, including but not limited to any one or more of the following plasticizers: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl glycolate, dicyclohexyl phthalate, bis (tridecyl) phthalate, di (2-ethyl) hexyl terephthalate; phosphates such as tricresyl phosphate, 2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. epoxyglycerides, epoxyfatty acid monoesters, epoxytetrahydrophthalates, epoxysoybean oil, epoxystearic acid (2-ethyl) hexyl ester, epoxysoybean oleic acid 2-ethylhexyl ester, 4, 5-epoxytetrahydrophthalic acid di (2-ethyl) hexyl ester, methyl buxine acetyl ricinoleate, dihydric alcohol esters, e.g. C _5～9 Glycol acid ester, C _5～9 Triethylene glycol acid diacetate; chlorine-containing compounds such as greening paraffins and chlorinated fatty acid esters; polyesters such as 1, 2-propanediol-based polyester oxalate, 1, 2-propanediol polyester sebacate; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol esters, and the like. Among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP), and the amount of the plasticizer used is not particularly limited, and is generally 5 to 20% by weight.

The foaming agent in the additive can enable the polymer sample to foam and form pores, so that a light, heat-insulating, sound-insulating and elastic polymer material is obtained, which comprises any one or any several foaming agents including but not limited to: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, diethyl ether, methyl chloride, methylene chloride, ethylene dichloride, dichlorodifluoromethane, trifluorochloromethane; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylene tetramine, N ' -dimethyl-N, N ' -dinitroso terephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamidate, azodiisobutyronitrile, 4' -oxybis-benzenesulfonyl hydrazide, trihydrazinotriazine, p-toluenesulfonyl semicarbazide, biphenyl-4, 4' -disulfonyl azide; foaming accelerators, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalene diphenol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, and the like. Among them, sodium hydrogencarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylene tetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitroso terephthalamide (foaming agent NTA), and physical microsphere foaming agent are preferable, and the amount of the foaming agent used is not particularly limited, and is generally 0.1 to 30% by weight.

The dynamic modifier in the additive can improve the dynamic property of the dynamic polymer, and is generally a compound with free hydroxyl or free carboxyl or capable of giving or receiving electron pairs, including but not limited to water, sodium hydroxide, alcohol, carboxylic acid, lewis base, lewis acid and the like. The addition of such auxiliaries allows the dynamic properties of the polymer to be adjusted in order to obtain optimum desired properties, the amount of dynamic regulator used being not particularly limited and generally ranging from 0.1 to 10% by weight.

The antistatic agent in the additive can guide or eliminate the accumulated harmful charges in the polymer sample, so that the harmful charges do not cause inconvenience or harm to production and life, and comprises, but is not limited to, any one or any several of the following antistatic agents: anionic antistatic agents such as alkyl sulfonate, sodium p-nonylphenoxy propane sulfonate, alkyl phosphate diethanolamine salt, potassium p-nonyldiphenyl ether sulfonate, phosphate derivatives, phosphate salts, polyoxyethylene alkyl ether alcohol phosphate, phosphate derivatives, fatty amine sulfonate, sodium butyrate sulfonate; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethylammonium chloride, dodecyl trimethylammonium bromide; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium acetate, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine acetate, sodium N-lauryl-N, N-dimeric ethylene oxide-N-ethyl phosphonate, N-alkylamino acid salts; nonionic antistatic agents such as fatty alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, trioxyvinyl ether phosphate, glycerol fatty acid esters; macromolecular antistatic agents such as polyallylamine N-quaternary ammonium salt substituents, poly 4-vinyl-1-acetonylpyridine phosphate-p-butylphenyl salt, and the like; among them, preferred are lauryl trimethyl ammonium chloride and alkyl phosphate diethanolamine salt (antistatic agent P), and the amount of the antistatic agent used is not particularly limited, and is generally 0.3 to 3% by weight.

The emulsifier in the additive can improve the surface tension between various constituent phases in the polymer mixed solution containing the additive to form a uniform and stable dispersion system or emulsion, and the emulsifier comprises any one or any several of the following emulsifiers: anionic, such as higher fatty acid salts, alkyl sulfonates, alkylbenzene sulfonates, sodium alkyl naphthalene sulfonates, succinate sulfonates, petroleum sulfonates, fatty alcohol sulfates, castor oil sulfate, sulfated butyl ricinoleate, phosphate esters, fatty acyl-peptide condensates; cationic, such as alkylammonium salts, alkylpyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic, such as fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol amine fatty acid amide, etc. Among them, sodium dodecylbenzenesulfonate, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM) are preferable, and the amount of the emulsifier used is not particularly limited, and is generally 1 to 5wt%.

The dispersing agent in the additive can disperse the solid flocculating groups in the polymer mixed liquid into fine particles to suspend in the liquid, uniformly disperse the solid and liquid particles which are difficult to dissolve in the liquid, and can prevent the sedimentation and agglomeration of the particles to form stable suspension, and the dispersing agent comprises any one or more dispersing agents of the following components: anionic, such as sodium alkyl sulfate, sodium alkylbenzenesulfonate, sodium petroleum sulfonate; a cation type; nonionic, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicate, condensed phosphate; polymer type such as gelatin, water-soluble glue, lecithin, sodium alginate, lignin sulfonate, polyvinyl alcohol, etc. Among them, sodium dodecylbenzenesulfonate, naphthalene-based methylenesulfonate (dispersant N) and fatty alcohol polyoxyethylene ether are preferable, and the amount of dispersant used is not particularly limited, but is generally 0.3 to 0.8wt%.

The colorants in the additive may be added to impart a desired color to the polymer product to increase the surface color, including but not limited to any one or more of the following: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. Lixol red BK, lake red C, perylene red, jia-base R red, phthalocyanine red, permanent magenta HF3C, plastic scarlet R and Kelolo Mo Gong BR, permanent orange HL, fast yellow G, sa Bao Plastic yellow R, permanent yellow 3G, permanent yellow H ₂ G. Phthalocyanine blue B, phthalocyanine green, plastic violet RL and aniline black; organic dyes such as thioisatin, vat yellow 4GF, petrolatum blue RSN, basic rose essence, oil soluble yellow, and the like. The amount of the colorant used is not particularly limited, and is generally 0.3 to 0.8wt%.

The fluorescent whitening agent in the additive can make the dyed matters obtain the effect of the flash luminescence similar to fluorite, and the fluorescent whitening agent comprises any one or any several of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazepine type, phthalimide type, etc. Among them, the fluorescent whitening agent is preferably sodium distyrene diphenyl disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) distyrene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1), and the amount of the fluorescent whitening agent used is not particularly limited, and is generally 0.002 to 0.03wt%.

The matting agent in the additive can make incident light diffuse reflection when reaching the surface of the polymer, and generate low-gloss matt and matting appearance, and comprises any one or any several matting agents of the following: and settling barium sulfate, silicon dioxide, water-containing gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like. Among them, silica is preferable, and the amount of the matting agent used is not particularly limited, and is generally 2 to 5% by weight.

The flame retardant in the additive can increase the flame resistance of the material, and comprises any one or any several of the following flame retardants: phosphorus systems such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate; halogen-containing phosphates, such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as chlorinated paraffin with high chlorine content, 1, 2-tetrabromoethane, decabromodiphenyl ether, and perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorobridge anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like. Among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate and antimony trioxide are preferable, and the amount of the flame retardant used is not particularly limited, but is generally 1 to 20% by weight.

The nucleating agent in the additive can accelerate crystallization rate, increase crystallization density and promote grain size refinement by changing crystallization behavior of the polymer, so as to achieve the purposes of shortening material forming period, improving transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and other physical and mechanical properties of the product, and the nucleating agent comprises any one or more of the following nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, sodium p-phenolsulfonate, silicon dioxide, dibenzylidene sorbitol and derivatives thereof, ethylene propylene rubber, ethylene propylene diene monomer rubber and the like. Among them, silica, dibenzylidene sorbitol (DBS) and ethylene propylene diene monomer are preferable, and the amount of the nucleating agent used is not particularly limited, and is generally 0.1 to 1wt%.

The rheological agent in the additive can ensure that the polymer has good brushing property and proper film thickness in the film coating process, prevent sedimentation of solid particles during storage and improve redispersibility, and comprises any one or any several rheological agents of the following: inorganic substances such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, fumed silica, water glass, colloidal silica; organometallic compounds such as aluminum stearate, aluminum alkoxides, titanium chelates, aluminum chelates; organic compounds such as organic bentonite, castor oil derivatives, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyvinyl alcohol, polyethylene wax, etc. Among them, organobentonite, polyethylene wax, hydrophobically modified alkali-swellable emulsion (HASE), alkali-swellable emulsion (ASE) are preferable, and the amount of the rheological agent to be used is not particularly limited, and is generally 0.1 to 1wt%.

The thickening agent in the additive can endow the polymer mixed liquor with good thixotropic property and proper consistency, thereby meeting the various requirements of stability, application performance and the like in the production, storage and use processes, and the thickening agent comprises any one or any several of the following thickening agents: low molecular substances such as fatty acid salts, fatty alcohol polyoxyethylene ether sulfate, alkyl dimethylamine oxide, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid isopropylamide, sorbitan tricarboxylic acid ester, glycerol trioleate, cocoamidopropyl betaine; high molecular substances such as bentonite, artificial hectorite, micro-powder silicon dioxide, colloidal aluminum, plant polysaccharides, microbial polysaccharides, animal proteins, alginic acid, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyether, and polyvinyl methyl ether urethane polymer. Among these, preferred are coconut diethanolamide and acrylic acid-methacrylic acid copolymer, and the amount of the thickener used is not particularly limited, but is generally 0.1 to 1.5% by weight.

The leveling agent in the additive can ensure the smoothness and uniformity of the polymer coating film, improve the surface quality of the coating film and improve the decoration, and comprises any one or any several of the following leveling agents: polyacrylate, silicone resin, and the like. Among them, the leveling agent is preferably polyacrylate, and the amount of the leveling agent used is not particularly limited, and is generally 0.5 to 1.5wt%.

The additive filler plays the following roles in the polymer material: (1) the shrinkage rate of the formed product is reduced, and the dimensional stability, the surface smoothness, the flatness or the matt property and the like of the product are improved; (2) adjusting the viscosity of the material; (3) meets the requirements of different properties, such as improving the impact strength and compression strength, hardness, rigidity and modulus of the material, improving the wear resistance, improving the heat deformation temperature, improving the electrical conductivity and thermal conductivity and the like; (4) the coloring effect of the pigment is improved; (5) imparting photostability and chemical resistance; (6) plays a role in capacity increase, can reduce cost and improve the competitive capacity of products in the market.

The additive filler is selected from any one or more of the following fillers: inorganic nonmetallic filler, metal filler and organic filler.

The inorganic nonmetallic fillers which can be added include, but are not limited to, any one or any several of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon black, quartz, mica powder, clay, asbestos fibers, orthoclate, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, graphene, carbon nanotubes, fullerenes, molybdenum disulfide, slag, flue dust, wood flour, shell powder, diatomaceous earth, red mud, wollastonite, silica-alumina carbon black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, lime mud, alkali mud, boron mud, (hollow) glass microspheres, foamed microspheres, glass powder, cement, glass fibers, carbon fibers, quartz fibers, carbon core boron fibers, titanium diboride fibers, calcium titanate fibers, carbon silica fibers, ceramic fibers, whiskers, and the like.

The metal filler which can be added comprises any one or any several of the following materials: powders, nanoparticles and fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof.

The organic filler which can be added comprises any one or any several of the following materials: fur, natural rubber, cotton linters, hemp, jute, flax, asbestos, shellac, lignin, protein, enzymes, hormones, raw lacquer, wood flour, shell powder, xylose, silk, rayon, vinylon, phenolic microbeads, resin microbeads, and the like.

Among them, the type of filler to be added is not limited, and is mainly determined according to the required material properties, and calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass beads, foam beads, glass fibers, carbon fibers, metal powder, natural rubber, protein, resin beads are preferable, and the amount of filler to be used is not particularly limited, and is generally 1 to 30wt%.

In the preparation process of the dynamic polymer material, additives which can be added are preferably antioxidants, light stabilizers, heat stabilizers, toughening agents, plasticizers, foaming agents, flame retardants and dynamic regulators. The filler which can be added is preferably calcium carbonate, barium sulfate, talcum powder, carbon black, glass beads, graphene, glass fibers and carbon fibers.

In the preparation of the dynamic polymer, the addition amount of each component raw material of the dynamic polymer is not particularly limited, and one skilled in the art can adjust according to the actual preparation and the target polymer properties.

In the preparation of the dynamic polymer, the dynamic polymer may be prepared by mixing the raw materials in a certain proportion by any suitable material mixing means known in the art, which may be a batch, semi-continuous or continuous process type of mixing; likewise, the dynamic polymer may be molded in a batch, semi-continuous or continuous process. The mixing means used include, but are not limited to, solution stirring and mixing, melt stirring and mixing, kneading, banburying, open mill, melt extrusion, ball milling, etc., among which solution stirring and mixing, melt stirring and mixing, and melt extrusion are preferable. The energy supply forms in the material mixing process include, but are not limited to, heating, illumination, radiation, microwaves, ultrasound. The molding mode includes, but is not limited to, extrusion molding, injection molding, compression molding, casting molding, calendaring molding and casting molding.

The method for producing a dynamic polymer by stirring and mixing a solution is generally to stir and mix raw materials in a reactor in a dissolved or dispersed form in respective solvents or in a common solvent. In general, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mold and placed for 0-48 hours at a temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample. In the process, the polymer sample in the form of solution, emulsion, paste, colloid, etc. can be prepared by selectively retaining the solvent according to the requirement, or the solid polymer sample in the form of film, block, etc. can be prepared by selectively removing the solvent.

When the compound (VI) and the compound (VII) are used as raw materials to prepare the dynamic polymer material by using the method, an initiator is added into a solvent to initiate polymerization in a solution polymerization mode to obtain the dynamic polymer, or a dispersing agent and an oil-soluble initiator are added to prepare a suspension to initiate polymerization in a suspension polymerization mode or a slurry polymerization mode to obtain the dynamic polymer, or an initiator and an emulsifying agent are added to prepare an emulsion to initiate polymerization in an emulsion polymerization mode to obtain the dynamic polymer. The methods of solution polymerization, suspension polymerization, slurry polymerization and emulsion polymerization employed are all well known and widely used polymerization methods by those skilled in the art and can be adapted according to the actual circumstances and are not developed in detail herein.

The solvent used in the preparation method is selected according to the actual conditions of reactants, products, reaction process and the like,including but not limited to any one or a mixture of solvents of the following: deionized water, acetonitrile, acetone, butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran, chloroform, methylene chloride, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, N-butyl acetate, trichloroethylene, mesitylene, dioxane, tris buffer, citric buffer, acetic buffer, phosphoric buffer, and the like; deionized water, toluene, chloroform, methylene chloride, 1, 2-dichloroethane, tetrahydrofuran, dimethylformamide, and a phosphoric acid buffer solution are preferred. In addition, the solvent can be selected from oligomer, plasticizer and ionic liquid; the oligomer includes, but is not limited to, poly (n-butyl acrylate) oligomer, liquid paraffin, etc.; the plasticizer may be selected from the classes of plasticizers in the additizable auxiliaries, which are not described in detail herein; the ionic liquid is generally composed of organic cations and inorganic anions, wherein the cations are generally alkyl quaternary ammonium ions, alkyl Ji ions, 1, 3-dialkyl substituted imidazole ions, N-alkyl substituted pyridine ions and the like; the anions are typically halogen ions, tetrafluoroborate ions, hexafluorophosphate ions, and also CF ₃ SO ₃ ^- 、(CF ₃ SO ₂ ) ₂ N ^- 、C ₃ F ₇ COO ^- 、C ₄ F ₉ SO ₃ ^- 、CF ₃ COO ^- 、(CF ₃ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₂ N ^- 、SbF ₆ ^- 、AsF ₆ ^- Etc. Wherein, when deionized water is used for preparing dynamic polymer and selecting to keep the dynamic polymer, hydrogel can be obtained; organogels can be obtained when dynamic polymers are prepared with organic solvents and selectively retained; when the oligomer is used for preparing dynamic polymer and selecting to keep the dynamic polymer, the oligomer swelling gel can be obtained; plasticizers can be obtained when they are used to prepare dynamic polymers and optionally to retain themSwelling the gel; when ionic liquids are used to prepare dynamic polymers and optionally retain them, ionic liquid swelling gels can be obtained.

In the above production method, the concentration of the compound liquid to be prepared is not particularly limited, and is preferably 0.1 to 10mol/L, more preferably 0.1 to 1mol/L, depending on the structure, molecular weight, solubility and desired dispersion state of the selected reactant.

The method for preparing dynamic polymer materials by melt stirring and mixing is generally to directly stir and mix raw materials in a reactor or stir and mix raw materials after heating and melting to react, and the method is generally used under the condition that the raw materials are gas, liquid or solid with lower melting point. In general, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mold and placed for 0-48 hours at a temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample.

When the compound (V) and the compound (VII) are used as raw materials to prepare the dynamic polymer material by the method, a small amount of initiator is also required to be added to initiate polymerization in a melt polymerization or gas phase polymerization mode to obtain the dynamic polymer. The methods of melt polymerization and gas phase polymerization used are well known and widely used by those skilled in the art, and can be adjusted according to the actual situation, and are not developed in detail here.

The specific method for preparing the dynamic polymer material by melt extrusion mixing is to add the raw materials into an extruder for extrusion blending reaction, wherein the extrusion temperature is 0-280 ℃, preferably 50-150 ℃. The reaction product can be directly cast and formed and then cut into a proper size, or the obtained extruded sample is crushed and then is prepared by an injection molding machine or a molding press. The injection molding temperature is 0-280 ℃, preferably 50-150 ℃, and the injection molding pressure is preferably 60-150MPa; the molding temperature is 0-280 ℃, preferably 25-150 ℃, more preferably 25-80 ℃, the molding time is 0.5-60min, preferably 1-10min, and the molding pressure is preferably 4-15MPa. The bars may be placed in a suitable mold and left at a temperature of 0-150 c, preferably 25-80 c, for 0-48 hours to obtain the final polymer sample.

In the preparation process of the dynamic polymer material, the selected organoboron compound (I), hydroxyl-containing compounds (II) - (IV), compound (V), compound (VI) and compound (VII) can be flexibly controlled in component selection and formula proportion, but reasonable design and combination are carried out according to the target material performance, the structure of the selected compound, the number of contained reactive groups and the molecular weight. Wherein the organoboron compound (I), hydroxyl-containing compounds (II) to (IV), compound (V), compound (VI) and compound (VII) to be added should ensure that the molar equivalent ratio of functional groups and/or other reactive groups in the reactant system is in a proper range. The molar equivalent ratio of the dihydroxy moieties contained in the organoboron compound (I), the hydroxyl-containing compounds (II) to (IV) and the compound (V) to the organoboron moiety functional groups is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, and still more preferably in the range of 0.8 to 1.2. When the molar equivalent ratio of the functional groups contained in the organoboron compound (I), the hydroxyl-containing compounds (II) to (IV) and the compound (V) is close to 1:1, a dynamic polymer with high reaction degree and good stability can be obtained; when the molar equivalent ratio of the functional groups contained in the organoboron compound (I), the hydroxyl-containing compounds (II) to (IV) and the compound (V) deviates from 1:1, a dynamic polymer material having good dynamic properties can be obtained. Similarly, when the compound (VI) and the compound (VII) are selected as the reaction components to prepare the dynamic polymer, the molar equivalent ratio of the other reactive groups in the reactant system should be in an appropriate range, and the molar equivalent ratio of the other reactive groups to be polymerized is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, and even more preferably in the range of 0.8 to 1.2. In the actual preparation process, the person skilled in the art can adjust the preparation process according to actual needs.

In the invention, the dynamic reversibility of organic borate ester bonds and optional supermolecule hydrogen bonds in the dynamic polymer is utilized, so that the polymer can show thickening responsiveness when being impacted by external force, and can achieve multiple absorption and dissipation of impact energy through reversible rupture of the organic borate ester bonds and the hydrogen bonds. For a non-crosslinked system, the thickening response produces complete viscosity loss enhancement, and strong energy absorption is achieved; for dynamic crosslinking systems, however, a viscous-elastic transition can be produced, while at the same time the viscous losses can be reduced. Therefore, polymer fibers, films, plates, elastomers, foams, gels, etc. having excellent energy absorbing effects can be prepared by appropriate component selection and formulation of the dynamic polymer. The dynamic polymer is used as an energy absorbing material for energy absorption, and can show good effects of damping, shock absorption, sound insulation, impact resistance and the like, so that the dynamic polymer has wide application in the fields of life, production, sports, leisure, entertainment, military, police, security, medical care and the like. In addition, the dynamic characteristics of the organic borate bond and the optional supermolecule hydrogen bond can also enable the obtained dynamic polymer to have good self-repairing property, recoverability and reusability, and prolong the service life of the dynamic polymer in the energy absorption application process; energy absorbing materials with shape memory function can also be designed and applied to specific occasions, such as personalized and customized energy absorbing protective tools. The energy absorption method based on the dynamic polymer is particularly suitable for impact resistance protection of human bodies, animal bodies, articles and the like, for example, the material is used as a protective tool to protect bodies in daily life, production and sports; the materials are prepared into explosion-proof tents, blankets, walls, laminated glass, sound-insulating and silencing materials, laminated plates and the like, and the explosion-proof protection is carried out on the articles; the product can be prepared into other protective articles/tools, and is applied to the aspects of air drop and air drop protection, automobile anti-collision, impact resistance protection of electronic and electric articles and the like.

The dynamic polymers of the present invention are described further below in connection with some embodiments. The present invention will be described in further detail with reference to specific examples, which are not intended to limit the scope of the invention.

Example 1

Adding 34g of acrylamide-phenylboronic acid-carbamate copolymer (prepared by taking methyl isocyanate and N- (2-hydroxyethyl) acrylamide as raw materials to react to prepare carbamate monomers, taking AIBN as an initiator, polymerizing acrylamide, 3-acrylamidophenylboronic acid and carbamate monomers through free radicals), heating 300mL of deionized water/THF mixed solvent to 50 ℃ to stir and dissolve, slowly adding 3.5g 1,1,3,3,5,5,7,7-octamethyl-1, 7-tetrasiloxydiol and 20mL of 0.3mol/L polyglycerol methanol solution, adding 2g of graphene, performing ultrasonic dispersion for 40min, adding 2.5mL of triethylamine, and continuously stirring and reacting for 2h at 50 ℃. Then adding 1.2g of sodium dodecyl benzene sulfonate, 0.7g of bentonite, 0.5g of stearic acid and 0.4g of oleic acid, and then adding 0.4g of organic bentonite, 0.3g of polydimethylsiloxane, 0.2g of dibutyltin dilaurate and 41mg of light stabilizer 770 into the mixture, heating, stirring and mixing the mixture uniformly to obtain gray black liquid with certain viscosity. Pouring a solution sample with certain viscosity into a proper mold, placing the sample in a 50 ℃ oven for drying for 24 hours to remove the solvent, cooling to room temperature and placing for 30 minutes to finally obtain a gray black membranous polymer sample. Preparing dumbbell-shaped sample bars with the size of 80.0X10.0X10.02 mm, carrying out tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, and the tensile strength of the sample is 3.89+/-0.11 MPa and the elongation at break is 289+/-23%; the conductivity was measured with a four-probe and found to be 2.45S/cm and 3.23S/cm in the stretched state. The polymer film has good strength, toughness, conductivity and stress response, and the stress strain curves at the early stage and the later stage of the stretching action are different, because the organic silicon borate bond has better dynamic property than the organic boric acid ring bond, the organic silicon borate bond is dissociated first, the organic boric acid ring bond is dissociated later, the gradual dissipation of energy is realized, and the toughness of the material is improved. The sample is broken after being broken, and then the broken recycled material is placed in a die at 50 ℃ to be pressed for 2-3 hours, so that the film can be formed again, the overall performance can reach more than 90% of the original performance, and the film can be used as a recyclable coating or protective film by utilizing the property of the film.

Example 2

Adding 18.9mL of a polyol compound (prepared by reflux-extracting 4-hydroxystyrene and formaldehyde serving as raw materials with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, using methanol as a solvent and triethylamine as a catalyst, carrying out thiol-olefin click addition reaction on the polyol compound and pentaerythritol tetrathioglycolate), 34mL of a toluene solution of 0.2mol/L methyl phenyl silicone oil, 1g of 200-mesh nano clay and 0.2mg of BHT antioxidant into a No. 1 reactor, carrying out ultrasonic dispersion for 30 minutes, and heating to 150 ℃ under stirring; then adding 3.11g of organic boron compound (prepared by carrying out a thio-ene click reaction on propenyl boric acid and 1,3, 5-triazine-2, 4, 6-trithiol) and 0.7mL of triethylamine, continuously reacting for 40-60min at 150 ℃, continuously reacting for 1h under the protection of nitrogen, pouring the mixture into a proper mold, placing the sample in a vacuum oven at 80 ℃ for 24h for further reaction, cooling to room temperature and placing for 30min, and finally obtaining a massive hard polymer material, wherein the surface of the polymer sample is smooth and has glossiness, and the sample can still be kept as it is after being thrown from a place with a height of 1.5m, and has good surface strength and rigidity. After crushing, the mixture is placed in a mold at 80 ℃ for 5 hours, and the sample can be reshaped. The sample was prepared into a dumbbell-shaped specimen of 80.0X10.0X12.0 mm in size, and was subjected to tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the sample was found to be 11.23.+ -. 0.54MPa. The stress-strain curves in the early stage and the later stage of the stretching effect are different, and the organic silicon borate ester bonds are better in dynamic property than the organic boric acid ring ester bonds, so that the organic silicon borate ester bonds are dissociated first, and then the organic boric acid ring ester bonds are dissociated, so that the gradual dissipation of energy is realized, and the toughness of the material is improved. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 1-3 hours, the section can be bonded by itself, and the performance of the molded sample reaches 89% of that of the original sample. The polymer can be used as a transparent organic polymer product by utilizing the characteristics of plasticity, reusability, recyclability and the like.

Example 3

34mL of 0.4mol/L acrylamide-borate copolymer (prepared by taking 1-aminoethylboric acid diisopropyl ester and acryloyl chloride as raw materials to react to prepare borate acrylamide monomers, then carrying out free radical polymerization on the borate acrylamide monomers and N, N-dimethylacrylamide to obtain a final product) in deionized water, uniformly mixing the solution and a small amount of acetic acid, slowly adding 5g of chlorosilane-terminated polybutadiene (prepared by taking hydroxyl-terminated 1, 3-polybutadiene and dichlorodimethylsilane as raw materials and toluene as a solvent and taking triethylamine as an absorption reaction HCl) and 19.2mL of 0.4mol/L polyethylene glycol aqueous solution, stirring and mixing for 30min, adding 3mL of triethylamine, carrying out reaction under the condition of nitrogen protection reflux, adding 0.3g of titanium alloy powder, 0.5g of ceramic powder and 0.2g of calcium sulfate after heating and uniformly stirring, and continuing to react for 4h. And pouring the polymer solution into a proper mold, placing the mold in a 50 ℃ oven for 24 hours for drying and further reacting, and finally obtaining a massive polymer sample. The sample was prepared into a dumbbell-shaped specimen of 80.0X10.0X12.0 mm in size, and was subjected to tensile test by a tensile testing machine at a tensile rate of 10mm/min, and the tensile strength of the specimen was 3.67.+ -. 0.31MPa and elongation at break was 286.+ -. 27%. The prepared polymer sample has smooth surface and good strength, and can be stretched in a certain range. In addition, after the sample surface is subjected to small scratches, the sample surface is placed in a mold at 80 ℃ and is attached for 1-3 hours under a certain pressure, the scratches disappear, and the sample surface has a good self-repairing effect and can be applied to manufacturing of impact-resistant ground mats.

Example 4

100mL of tetrahydrofuran solvent, 18g of cyclohexane boron compound-terminated polydimethyl silicone oil (prepared by using 3-aminocyclohexane boric acid as a raw material and dibromo-terminated polydimethyl silicone oil (with the molecular weight of about 3000) through hydrocarbylating reaction) are added into a No. 1 reactor, 2.15g of isopropyl boric acid and 9mL of modified hydroxyl silicone oil (prepared by using cyanuric acid and 6-chloro-1-hexene as raw materials and carrying out a reaction under the catalysis of potassium carbonate to obtain an olefin monomer containing hydrogen bond groups, and then the olefin monomer is subjected to hydrosilylation with methyl hydrogen-containing hydroxyl silicone oil with the molecular weight of 20,000 under the catalysis of Pt) and 2mL of triethylamine are added into the reactor under the stirring state, and the reaction is continued for 4h under the protection of nitrogen. In the reaction process, the solution viscosity is continuously increased, after the reaction is finished, the polymer solution is poured into a proper mold, and is placed in a vacuum oven at 80 ℃ for drying for 24 hours to remove the solvent, and then cooled to room temperature and placed for 30 minutes, so that a polymer solid sample in a block-shaped hard gel state is finally obtained. The sample was prepared into a dumbbell-shaped bar of 80.0X10.0X12.0 mm in size, and was subjected to tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the sample was measured to be 2.18.+ -. 1.12MPa. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 82% of the original sample. The polymer product can be used as a sealing gasket and applied to sealing of building caulking and sealing treatment of electronic elements.

Example 5

20g of phenylboronic acid modified silicone rubber (prepared from methyl vinyl silicone rubber and 2-mercaptoethylamine serving as raw materials, triethylamine serving as a catalyst and through thiol-olefin click addition reaction to prepare an intermediate product, then synthesizing the intermediate product with 2-formylcyclohexane neopentyl glycol borate through Petasis reaction to obtain a final product), 20g of silanol modified silicone rubber (prepared from methyl silicone rubber and gamma-mercaptopropyl methyl dihydroxysilane serving as raw materials, and DMPA serving as a photoinitiator, under the condition of ultraviolet irradiation, preparing the intermediate product through thiol-olefin click addition reaction, then hydrolyzing to obtain the final product), and an acrylic acid-dihydroxyacrylamide copolymer (prepared from N- (2- (3, 4-dihydroxycyclohexyl) ethyl) acrylamide and acrylic acid through free radical polymerization copolymerization by taking AIBN serving as an initiator) are added into a small internal mixer to be mixed for 30min, adding 12g of white carbon black, 17g of titanium dioxide, 3.2g of ferric oxide, 3g of carbon nano tube and 0.05g of silicone oil, continuously mixing for 6 hours, taking out the sizing material after fully and uniformly mixing the additive and the sizing material, placing the sizing material in a proper mold, placing the sizing material in a vacuum oven at 80 ℃ for 24 hours for further reaction, cooling the sizing material to room temperature, placing the sizing material for 30 minutes, taking out a sample from the mold, finally obtaining a soft dynamic plugging rubber material which has good plasticity, can be prepared into products with different shapes according to the size of the mold, has different conductivities under the action of unused tension or pressure while having good toughness, and has stress responsiveness. In addition, the polymer has a large number of dynamic bonds, so that the polymer is very convenient to recycle or treat waste, after the stretch-broken polymer sample is recycled, the polymer is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 1-3 hours, the section can be bonded by itself, the formed sample can reach 90% of the original sample. The silicon rubber damping vibration attenuation sheet can be manufactured into silicon rubber damping vibration attenuation sheets by utilizing the functional characteristics of the silicon rubber damping vibration attenuation sheets and is applied to the fields of stress sensors, electronics and electrics, medical appliances, automobile industry and the like.

Example 6

Dissolving a certain amount of polyol compound in toluene solvent to prepare 0.2mol/L solution, taking 10mL of sample from the solution, adding the sample into a No. 1 reactor, and adding 3mg of BHT antioxidant; 1, 8-dihydroxyanthracene was dissolved in toluene solvent to prepare a 0.2mol/L solution, and 10mL of the solution was taken therefrom and fed into reactor No. 1. 16g of 1, 4-phenylene bisboric acid was added with stirring, the reaction was carried out at 80℃and, as stirring proceeded, the solution viscosity increased, and then the polymer sample was poured into a suitable mold, and the solvent was evaporated at room temperature for 12 hours. After that, the polymer sample was left flat in a vacuum oven at 80 ℃ to remove the residual solvent, and the resulting polymer sample had a greater rigidity but a brittle texture. The sample was prepared into a dumbbell-shaped specimen with a size of 80.0X10.0X12.0 mm, and was subjected to a tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the specimen was measured to be 6.32.+ -. 0.29MPa and the elongation at break was measured to be 42.+ -. 6%. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, the sample after being formed is reshaped, the performance of the formed sample reaches 80% of that of the original sample, and the formed sample can be used as a recyclable rigid gasket by utilizing the property of the formed sample.

Example 7

Dissolving a certain amount of 1, 7-heptanediol in a methanol solvent to prepare a solution of 0.4 mol/L; taking a certain amount of compound (II) containing dihydroxy moieties (prepared by taking tetraallyloxyethane and 3-mercapto-1, 2-propanediol as raw materials and methanol as a solvent and triethylamine as a catalyst through thiol-olefin click addition reaction) and dissolving the compound (II) in the methanol solvent to prepare a solution of 0.2 mol/L; 20mL of a compound (II) solution containing dihydroxy moieties, 25g of boric acid grafted modified polypropylene (dicumyl peroxide is used as an initiator, maleic anhydride is used for grafting modified low molecular weight polypropylene, p-toluenesulfonic acid is used as a catalyst, 1-aminoethylboric acid and maleic anhydride are used for grafting polypropylene to obtain a final product), 50g of polybutyl acrylate oligomer and 5g of cellulose nanocrystals are respectively added into a No. 1 reactor, and stirring is slowly carried out at room temperature for about 40-50min, the solution starts to have a certain viscosity, at this time, a sample is poured into a proper mold, and then cooled to room temperature and placed for 30min, so that a transparent film-shaped oligomer swelling gel dynamic polymer sample is finally obtained. The sample was prepared into dumbbell-shaped bars of 80.0X10.0X10.02 mm in size, and was subjected to tensile test by a tensile tester at a tensile rate of 50mm/min, and the tensile strength of the sample was measured to be 6.32.+ -. 0.76MPa and the elongation at break was 468.+ -. 25%. The polymer film is soft in texture, has good strength and toughness, can be stretched in a certain range, and has good tear resistance. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 84% of the original sample. The material can be recycled, and can be used as a recyclable packaging film or a product for film pasting by utilizing the property of the material.

Example 8

Taking a certain amount of acrylamide-dihydroxyl radical copolymer (prepared by taking 4-hydroxystyrene and formaldehyde as raw materials, refluxing the raw materials with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, taking AIBN as an initiator, and carrying out free radical polymerization copolymerization on the 2- (hydroxymethyl) -4-vinylphenol and N, N-dimethylacrylamide) to prepare a solution of 0.2 mol/L; taking a certain amount of acrylamide-phenolic hydroxyl copolymer (taking p-hydroxystyrene and acrylamide as raw materials, using AIBN as an initiator to polymerize the copolymer, and then reacting amino groups in the copolymer with ethyl diisocyanate to obtain a product), dissolving the product in deionized water, and preparing a solution of 0.2 mol/L. Respectively taking 20mL of acrylamide-dihydroxyl primitive copolymer solution and acrylamide-phenolic hydroxyl copolymer solution, adding the solution into a No. 1 reactor, uniformly mixing by stirring, stirring for 20-30min, adding 15g of borate modified polystyrene (prepared by using AIBN as an initiator and using styrene and 4-vinylphenylboronic acid propylene glycol ester through free radical copolymerization), 50mg of nano silicon dioxide with the particle size of 25nm and 150mL of toluene solvent, ultrasonically dispersing for 40min, heating to 60 ℃ for dissolving by stirring, adding a small amount of 20% acetic acid aqueous solution, and continuously reacting for 4h to finally obtain the massive hydrogel dynamic polymer with good mechanical strength and poor elasticity and toughness. The dumbbell type sample is manufactured into dumbbell type sample bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 10mm/min, the tensile strength of the sample is 13.75+/-1.23 MPa, the elongation at break is 98+/-5%, after the broken polymer sample is recovered, good pressure is applied, the sample bars are placed in a water bath with the temperature of 60 ℃ for heating for 2-3h, the section can be bonded by itself, the sample bars are reshaped, and the performance of the shaped sample reaches 86% of that of the original sample. The material has good mechanical property and recoverability, and can be used as an orthopedic correction product by utilizing the property of the material.

Example 9

Adding 150mL of chloroform solvent into a No. 1 reactor, introducing nitrogen to remove water and oxygen for 1h, adding 13.2g of partially hydrolyzed borate modified polybutadiene (taking amino-terminated 1, 3-polybutadiene, (bromomethyl) diisopropyl borate as a raw material, preparing an intermediate product through hydrocarbylating reaction, then taking DMPA as a photoinitiator with 3-amino-N- (2-mercaptoethyl) propionamide, carrying out thiol-olefin click addition reaction under ultraviolet irradiation condition, reacting amino in the obtained product with isopropyl isocyanate, finally placing the reaction product into deionized water with a certain temperature to carry out partial hydrolysis to prepare 32g of ethylene-vinyl alcohol copolymer, 26mL of 0.4mol/L organic boron compound (taking 1-hydroxy borone as a raw material, preparing 2-bromo-1-hydroxy borone through addition reaction with hydrobromic acid, taking 1,3, 5-triacrylhexahydro-1, 3, 5-triazine and 2-amino ethyl amine as raw materials, taking AIBN as a thiol initiator, preparing a triethylamine as a catalyst, preparing a solution by stirring uniformly with 2mL of 2-hydroxy borone after carrying out the steps of reaction at a temperature of intermediate product, preparing 2-bromo-1, 2-hydroxy borone, and stirring the solution under a small amount of 2mL of 2 h, continuously stirring, and carrying out the steps of reacting with 2g of 2-hydroxy borone under stirring conditions. Then pouring the reaction liquid into a proper mold, placing the mold in a vacuum oven at 60 ℃ for 24 hours for further reaction and drying, cooling to room temperature and placing for 30 minutes to finally obtain a gelatinous polymer material, wherein the sample has good elasticity and toughness and can be stretched in a larger range. Preparing dumbbell-shaped sample bars with the size of 80.0X10.0X12.0 mm, carrying out tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, and the tensile strength of the sample is 5.32+/-0.36 MPa and the elongation at break is 447+/-34%; the conductivity was measured with a four-probe and found to be 2.78S/cm, and 4.35S/cm in the stretched state. The polymer film has rubber characteristic, good toughness, conductivity and stress response, and in addition, the prepared product has good plasticity, can be placed in moulds with different shapes according to actual needs, and can be molded into polymer products with different shapes according to the moulds by slightly applying certain stress under certain temperature conditions. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 85% of the original sample. In this embodiment, the polymer may be used as a resilient gasket, stress sensor or cushion pad.

Example 10

13g of a partially hydrolyzed acrylamide-haloborane copolymer (prepared by reacting 1-aminoethylboric acid diisopropyl ester and acryloyl chloride as raw materials to prepare a borate acrylamide monomer 1, reacting isocyanate ethyl acrylate and ethylamine as raw materials to prepare a monomer 2, polymerizing the monomer 1, the monomer 2 and N, N-dimethylacrylamide by free radicals, finally placing the product into deionized water at a certain temperature to partially hydrolyze to obtain a final product), 80mL of toluene, stirring at 60 ℃ until the final product is completely dissolved, then adding 10mL of 0.3mol/L dihydroxy group terminated polyethylene (prepared by polymerizing ethylene to prepare vinyl terminated polyethylene by using a Zr-FI catalyst and then reacting the vinyl terminated polyethylene with 3-mercapto-1, 2-propanediol by thiol-olefin click addition reaction, wherein the addition reaction catalyst is triethylamine) toluene solution, 0.5g of carbon nano tubes and 3.3g of 1, 5-pentanediol, and continuously reacting for 4 hours in a water bath at 60 ℃. Pouring a solution sample with certain viscosity into a proper mold, cooling to room temperature and standing for 30min to finally obtain the transparent organic gel dynamic polymer sample. The sample was cut into dumbbell-shaped bars of 80.0X10.0X10.02 mm in size, and was subjected to tensile testing by a tensile testing machine at a tensile rate of 50mm/min, and the tensile strength of the sample was measured to be 2.56.+ -. 0.23MPa and the elongation at break was measured to be 345.+ -. 35%. The organogel is tough and soft, has good toughness, can be stretched and stretched to a large extent, has good toughness, and has different conductivities under the action of unused tensile force or pressure, so that the organogel has stress responsiveness. In addition, after the sample is broken, the sample is placed in a die at 50 ℃ for lamination for 3 hours, a new sample with 93% of the comprehensive performance of the original sample can be obtained, and the material can be used as a stress sensor.

Example 11

15mL of 0.2mol/L dendritic polyol compound (methanol is taken as a solvent, triethylamine is taken as a catalyst, triallylamine and 1, 2-ethanedithiol are subjected to thiol-olefin click addition reaction to prepare a first intermediate product, then the first intermediate product and triallylamine are subjected to thiol-olefin click addition reaction to prepare a second intermediate product, then the second intermediate product and 1, 2-ethanedithiol are subjected to thiol-olefin click addition reaction to prepare a third intermediate product, then the third intermediate product and triallylamine are subjected to thiol-olefin click addition reaction to prepare a fourth intermediate product, finally the third intermediate product and 3-mercapto-1, 2-propanediol are subjected to thiol-olefin click addition reaction to prepare a final product), 50mL of 0.1mol/L modified polynorbornene (prepared by vinyl boric acid and cyclopentadiene and DielR-Alder reaction, then the second intermediate product and cyclopentadiene are subjected to Diels-Alder reaction to prepare amido modified norbornene, and the first intermediate product and the final intermediate product are subjected to polymerization reaction with 3-mercapto-1, 2-propanediol and the final product are prepared into the final product of 3.7 g of the modified benzol by using methyl-aluminum borate as a methyl-terminated polybutadiene, and the final product is prepared by polymerizing the final product and the final product. After ultrasonic dispersion for 40min, stirring uniformly at 60 ℃, dropwise adding a small amount of 1mol/L NaOH solution, and continuing stirring at 60 ℃. After slowly stirring for about 30-40min, pouring the solution sample into a proper mold, placing the sample in a 50 ℃ oven for drying for 24h to remove the solvent, cooling to room temperature and placing for 30min, preparing the sample into dumbbell-shaped bars with the size of 80.0x10.0x2.0 mm, and performing tensile test by using a tensile testing machine at the tensile rate of 10mm/min, wherein the tensile strength of the sample is 7.24+/-0.34 MPa and the elongation at break is 734+/-57%. The stress-strain curves in the early stage and the later stage of the stretching effect are different, and the organic boric acid anhydride bond has better dynamic property than the organic boric acid cyclic ester bond, so that after the hydrogen bond is dissociated, the organic boric acid anhydride bond is dissociated first, the organic boric acid cyclic ester bond is dissociated later, the gradual dissipation of energy is realized, and the toughness and the energy absorption of the material are improved. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 88% of the original sample. In this embodiment, the polymer sample may be made into a sealant or recyclable elastic pellet toy, which can exhibit good toughness and elasticity, and may be pressed into products of different shapes and sizes as needed, and broken or no longer needed samples may be recycled to make new products for use.

Example 12

Taking 24g of boric acid grafted modified polyethylene (prepared by taking ethylene-vinyl alcohol copolymer as a raw material, reacting the ethylene-vinyl alcohol copolymer with acryloyl chloride to obtain an ethylene copolymer with double bonds in side chains, then carrying out free radical copolymerization reaction on the ethylene copolymer and 2-mercaptoethanol pinacol ester by using a thio-ene click reaction, mixing 22g of boric acid mono-terminated polyethylene oxide (prepared by uniformly mixing methyl vinyl boric acid and 2-mercaptoethanol by using a thio-ene click reaction, using boron trifluoride diethyl ether as a catalyst, initiating ring-opening polymerization of ethylene oxide, using methyl chloride to terminate the end), 32g of macromolecular mono-alkanol compound (prepared by carrying out a free radical copolymerization reaction on a product and 3-butene-1-ol and methyl acrylate under the action of an initiator AIBN), adding 0.8g of stearic acid, 0.1g of antioxidant 1010, 0.2g of di-n-butyltin dilaurate and 0.5g of dimethyl silicone oil into a small extruder, carrying out extrusion at the temperature of a small extruder and using a sample of 150 ℃ to obtain a sample, carrying out injection molding under the conditions of 150 ℃ and further carrying out dynamic extrusion polymerization at the temperature of 150 ℃ under the conditions of a sample injection molding, and then carrying out injection molding under the conditions of 150 h. The sample was prepared into dumbbell-shaped bars of 80.0X10.0X12.0 mm in size, and was subjected to tensile test by a tensile testing machine at a tensile rate of 10mm/min, and the tensile strength of the sample was found to be 4.68.+ -. 0.35MPa and the elongation at break was found to be 495.+ -. 64%. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 1-2 hours, the section can be bonded by itself, and the sample performance after being formed reaches 87% of the original sample. In this example, a polymer sample can be used as a flame retardant additive for plastic molding.

Example 13

18g of phenylboronic acid modified polycarbonate (limonene oxide is extracted from orange peel and is polymerized with carbon dioxide under the catalysis of beta-diimine zinc to obtain polycarbonate PLimC, the polycarbonate PLimC is polymerized with [4- (mercaptomethyl) phenyl ] neopentyl glycol ester and 6-thiosemicarbazide pyrimidine through a thio-ene click reaction, amino and hydroxyl in the product are reacted with isopropyl isocyanate to obtain the product), 0.5g of nano silicon dioxide with silicon hydroxyl on the surface, 5.3g of acrylamide-dihydroxy primitive copolymer (prepared by taking 4-hydroxystyrene and formaldehyde as raw materials, refluxing the raw materials with zinc nitrate hexahydrate for 24h to synthesize 2- (hydroxymethyl) -4-vinylphenol, AIBN is taken as an initiator, 2- (hydroxymethyl) -4-vinylphenol and N, N-dimethylacrylamide are polymerized and copolymerized through free radicals), 7.2g of boric acid modified polystyrene (prepared by taking AIBN and 4-vinylphenylboronic acid through free radical copolymerization), 1g of 50nm of phenylboronic acid, the product is added into a toluene mold at the temperature of 50 ℃ and the temperature of 50 mg, the product is heated to be uniformly stirred for 24 mg of sodium in a mold under the condition of 50 mg of toluene, and the final reaction is heated to obtain the product after the final reaction is stirred for 24h, and the product is heated to be stirred and stirred uniformly in a mold for 24 mg of sodium in a mold. The sample was prepared into a dumbbell-shaped specimen with a size of 80.0X10.0X12.0 mm, and was subjected to a tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the specimen was measured to be 12.34.+ -. 0.98MPa and the elongation at break was measured to be 55.+ -. 9%. The stress-strain curve of the product in the embodiment has four stages, namely, a hydrogen bond-organic silicon borate bond-organic boric anhydride bond-organic boric acid cyclic ester bond is sequentially dissociated step by step, so that the step-by-step dissipation of energy is realized, and the strength and the good dynamic performance of the material are improved. After the stretch-broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 80 ℃ under good pressure, heated and placed for 2-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 95% of the original sample. In this embodiment, the functional properties exhibited by the polymer sample are utilized as a kind of sealing plug.

Example 14

54g of borate copolymer (prepared by taking AIBN as an initiator and carrying out free radical polymerization on 1-allyl-2, 4-dioxo-1, 2,3, 4-tetrahydro-5-pyrimidine nitrile and propylene-based boric acid diisopropyl ester), 23g of sodium alginate, 4g of diphenylsilane, 3g of 4-hydroxyphenylethanol, 70g of dioctyl phthalate, 8g of MBS toughening agent, 2g of stearic acid, 0.5g of antioxidant 168, 0.4g of antioxidant 1010, 0.3g of dioctyl tin dilaurate and 1g of simethicone are uniformly mixed, the temperature is raised to 80 ℃, stirring reaction is carried out for 2 hours, then the mixture is taken out, placed in a mold, and placed for 6 hours under the protection of nitrogen at 50 ℃ for subsequent reaction, and finally the plasticizer swelling gel dynamic polymer is obtained. The dumbbell type sample is manufactured into dumbbell type sample bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 10mm/min, the tensile strength of the sample is 13.24+/-0.79 MPa, the elongation at break is 84+/-8%, the stress-strain curve of the product in the embodiment has four stages, and the hydrogen bond-organic silicon borate ester bond-organic boric acid cyclic ester bond-organic boric acid monoester bond are sequentially dissociated step by step, so that the step dissipation of energy is realized, and the strength and the good dynamic performance of the material are improved. In addition, after the stretch broken polymer sample is recovered, the polymer sample is placed in a vacuum oven at 60 ℃ under good pressure, heated and placed for 1-3 hours, the section can be bonded by itself, and the sample performance after being formed reaches 93% of the original sample. In this embodiment, the polymer sample may be used as a gel tube, which may be recycled after breakage.

Example 15

55g of phenylborate grafted modified polyvinyl alcohol (which is taken as a raw material and reacts with acryloyl chloride to obtain a copolymer with double bonds in side chains, and then the copolymer reacts with 2-mercaptophenylborate pinacol ester to obtain a final product through thio-ene click reaction), and 13g of acrylamide-boric acid copolymer (which is taken as a raw material and reacts with 1-aminoethyl diisopropyl borate and acryloyl chloride to obtain borate acrylamide monomer 1; the method comprises the steps of preparing monomer 2 by taking isocyanate ethyl acrylate and ethylamine as raw materials, preparing a final product by free radical polymerization of monomer 1, monomer 2 and N, N-dimethylacrylamide), 17g of oxazolidone-catechol copolymer (after allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidone are dissolved in toluene according to a molar ratio of 1:1, preparing allyl oxazolidone by taking potassium carbonate as a catalyst and tetrabutylammonium bromide as a phase transfer agent, preparing the allyl oxazolidone by taking the allyl oxazolidone and tetrabutylammonium bromide as a phase transfer agent, carrying out free radical polymerization on the allyl oxazolidone and N-isopropylacrylamide and catechol under the action of Benzoyl Peroxide (BPO), preparing 5g of isoliquiritigenin, 10g of AC foaming agent, 2g of zinc oxide, 8g of calcium carbonate, 0.5g of stearic acid, 0.2g of antioxidant 168, 0.3g of antioxidant 1010 and 0.5g of di-N-butyltin dilaurate, carrying out banburying and blending at a blending temperature of 100 ℃ for 10min, taking out a sample out a twin roll, carrying out a pre-roll, carrying out a cross-linking reaction in a drying sheet, carrying out a vacuum drying sheet, carrying out a pre-drying sheet, carrying out a cooling reaction, and carrying out a drying sheet in a vacuum drying oven, and carrying out a cooling and standing in a drying oven for 80 h, then cooled to room temperature and left for 30min. Taking out the mixed sample sheet from the die, shearing the mixed sample sheet, taking a proper amount of the mixed sample sheet, placing the mixed sample sheet into a proper die, and performing foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 130-140 ℃, the molding time is 20-30min, and the pressure is 10MPa, so that a soft polymer foam sample is finally obtained, and the soft polymer foam sample has good softness and can be stretched in a large range. The sample was prepared into a dumbbell-shaped specimen of 80.0X10.0X12.0 mm in size, and was subjected to tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the specimen was 14.76.+ -. 0.45MPa and elongation at break was 27.+ -. 2%. After the polymer material is cut off, the polymer material is placed in a mould at 100 ℃ and subjected to pressure application to be formed again, the performance of the formed sample reaches 90% of that of the original sample, and the self-repairing property of the formed sample can be used repeatedly. In this embodiment, the dynamic polymer material can be used to make a recyclable foam packaging material.

Example 16

Adding 25g of an organoboron compound (prepared by taking 4-hydroxyphenylboronic acid pinacol ester and 1, 6-hexamethylene diisocyanate as raw materials for reaction) into a dry and clean reaction bottle, adding 200mL of THF solvent, heating to 60 ℃ for stirring and dissolving, then dropwise adding a small amount of 20% acetic acid aqueous solution, weighing 4.32g of diphenylsilanediol into the mixed solution, then adding 2.6g of 1,1' - (1, 3-phenylene) bis (ethane-1, 2-diol) and 2.5g of soybean flavone, continuously reacting for 4 hours, placing the sample into a 50 ℃ oven for drying for 24 hours, cooling to room temperature for 30 minutes, chopping the sample, taking 25g of the sample and 25g of phenylboronic acid copolymerization modified isoprene rubber (prepared by taking AIBN as an initiator, and adding 7g of white carbon black, 8g of 0.1g of barium stearate and 0.3g of stearic acid into a small internal mixer for mixing for 20 minutes, and continuously mixing for 20 minutes. And after the additive and the sizing material are fully and uniformly mixed, taking out the mixed material, cooling, placing the mixed material into a double-roller machine, pressing the mixed material into a sheet, cooling at room temperature, and cutting the sheet. The prepared polymer sheet is soaked in water at 90 ℃ for crosslinking, then taken out, placed in a vacuum oven at 80 ℃ for 6 hours for further reaction and drying, then cooled to room temperature and placed for 30 minutes, and a sample is taken out from a die to finally obtain a rubbery dynamic polymer material which has good plasticity, can be prepared into products with different shapes according to the die size, can be stretched and extended in a large range, and shows very excellent stretching toughness. The dumbbell type sample is manufactured into dumbbell type sample bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 10mm/min, the tensile strength of the sample is 8.13+/-0.87 MPa, the elongation at break is 55+/-5%, and four types of organic borate dynamic bonds, side hydrogen bonds and skeleton hydrogen bonds are dissociated step by step according to the dynamic property of the organic borate dynamic bonds, the side hydrogen bonds and the skeleton hydrogen bonds to dissipate energy, so that the strength of the material is greatly improved. After scoring the surface of the polymeric material with a blade, the sample was allowed to self-repair by placing it in a vacuum oven at 80 ℃ for 2 hours, where the score disappeared (optionally slightly wetting the surface). The polymer material can be used to make instrument transport protective housings.

Example 17

25g of boric acid modified silicone rubber (prepared by dripping 4-bromobutyl boric acid into hot thiourea ethanol solution and heating and refluxing with potassium hydroxide aqueous solution to obtain a product), DMPA (prepared by thiol-olefin click addition reaction under ultraviolet irradiation condition) and 15g of silanol modified silicone rubber (prepared by methyl vinyl silicone rubber and gamma-mercaptopropyl methyl dimethoxy silane, prepared by thiol-olefin click addition reaction and DMPA (prepared by intermediate product and then hydrolyzing under ultraviolet irradiation condition) are taken as raw materials, 13g of dihydroxy primitive modified silicone rubber (prepared by methyl vinyl silicone rubber and 3-mercapto-1, 2-propanediol, prepared by thiol-olefin click addition reaction under triethylamine catalysis condition), 6g of conductive carbon black, 3g of 1000-mesh conductive carbon black, 2.7g of ferric oxide and 0.3g of silicon oil are added into a small-sized mixer to be mixed for 40min, so that the additive and sizing material are uniformly mixed, and then the mixture is taken out under the condition of 120 h under the condition. And then taking out the sizing material, placing the sizing material in a proper mold, placing the sizing material in a vacuum oven at 80 ℃ for 4 hours, and then forming the sizing material under the pressure of 10MPa to obtain the silicone rubber-based dynamic polymer material. Dumbbell-shaped bars with the size of 80.0X10.0X12.0 mm are manufactured by using a die, and are subjected to tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, and the tensile strength of the sample is 6.35+/-0.68 MPa and the elongation at break is 1224+/-121%. The polymer material has good strength and toughness, and the conductivity of the polymer material is measured to change according to the tensile or compressive state of the material, which indicates that the material has stress responsiveness; after the polymer material is cut off, the polymer material is placed in a mould at 100 ℃ and subjected to pressure application to be formed again, the performance of the formed sample reaches 93% of that of a raw sample, the polymer material can be stretched in a large range, and the obtained polymer material can be manufactured into an antistatic sealing ring, a high-strength stress sensing material or a potting material.

Example 18

25g of borate modified polystyrene (prepared by using AIBN as an initiator and using styrene and 4-vinylphenylboronic acid propylene glycol ester through free radical copolymerization), 21g of poly-p-styrol and 18g of silane modified styrene-maleic anhydride copolymer (prepared by using p-toluenesulfonic acid as a catalyst and reacting 3-aminopropyl methyl dimethoxy silane with styrene-maleic anhydride copolymer and hydrolyzing the product), 12g of AC foaming agent, 5g of zinc oxide, 7g of calcium carbonate, 0.5g of stearic acid, 0.2g of antioxidant 168, 0.3g of antioxidant 1010 and 0.5g of di-n-butyltin dilaurate are weighed, uniformly mixed, added into a small internal mixer for banburying and blending, wherein the blending temperature is 100 ℃, the blending time is 30min, the sample is taken out, pressed into a sheet in a double-roll machine, cooled at room temperature, the cut sheet is immersed in water at 90 ℃, pre-crosslinked, then taken out, placed in a vacuum oven at 80 ℃ for 6h for further reaction, dried and placed at room temperature for 30min. Taking out the mixed sample sheet from the die, shearing the mixed sample sheet, taking a proper amount of the mixed sample sheet, placing the mixed sample sheet into a proper die, and performing foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 130-140 ℃, the molding time is 10-15min, and the pressure is 10MPa, so that a semi-rigid polymer foam sample is finally obtained, has good softness, and can be stretched in a large range. The sample was prepared into a dumbbell-shaped specimen with a size of 80.0X10.0X12.0 mm, and was subjected to a tensile test by a tensile tester at a tensile rate of 10mm/min, and the tensile strength of the specimen was 8.25.+ -. 0.56MPa and the elongation at break was 25.+ -. 2%. After the polymer material is cut off, the polymer material is placed in a die at 60 ℃ to apply pressure for reshaping, the property of the molded sample reaches 92% of that of the original sample, and the self-repairing property of the molded sample can be used repeatedly. In this embodiment, the prepared material has self-repairable property, and can be used for manufacturing wall protection materials.

Example 19

Adding 5.6g of an organoboron compound (prepared by using diisopropyl propenyl borate and 1,3, 5-triazine-2, 4, 6-trithiol as an initiator and using AIBN as a catalyst and triethylamine through a thio-ene click reaction), 4.1g of a four-arm compound (a) blocked by boric acid (prepared by using 2-aminomethyl phenylboronic acid and tetrabromo quaternary amyl alcohol through a hydrocarbylation reaction), 0.7g of graphene and 100mL of DMF solvent into a No. 1 reactor, ultrasonically dispersing for 40min, heating to 80 ℃ again for stirring and dissolving, dropwise adding a small amount of 20% acetic acid aqueous solution, continuously stirring and mixing for 30min, slowly adding 12.5mL of hydroxyl-blocked methylphenyl silicone oil (with a molecular weight of about 12,000), stirring and mixing for 30min, adding 2mL of triethylamine, continuously stirring and reacting for 3h at 80 ℃, placing the polymer in a 80 ℃ vacuum oven for drying for 24h, removing the solvent, and cooling to room temperature for 30min. Preparing the sample into dumbbell-shaped bars with the size of 80.0X10.0X12.0 mm, carrying out tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, and the tensile strength of the sample is 8.34+/-1.46 MPa and the elongation is 51+/-5%, so that the sample can be used as an antistatic protective shell; after cutting the polymer material, placing the polymer material in a mould at 60 ℃ and applying pressure for 1-2 hours, and then reforming, wherein the performance of the molded sample reaches 95% of that of the original sample.

Example 20

Adding 27g of boric acid-terminated three-arm polysiloxane (3-bromo-4- (bromomethyl) benzaldehyde is used as a raw material, reacting the raw material with methyltriphenylphosphorus bromide and potassium tert-butoxide at room temperature for 24 hours, heating to 100 ℃ and reacting the raw material with tert-butyldimethylsilyl chloride and imidazole in a DMF solvent for 20 hours, reacting the raw material with methanol and methoxymethyl chloride in the tetrahydrofuran solvent for 4 hours, heating to 60 ℃ for 3 hours, adding tributyl borate for room temperature for 8 hours, purifying to obtain 2- (hydroxymethyl) phenylboronic acid cyclic monoester ethylene, synthesizing three-end hydrogen-based polysiloxane by a ring-opening polymerization method by using octamethyl cyclotetrasiloxane and phenyl tris (dimethylsiloxy) silane as raw materials and using concentrated sulfuric acid as catalysts, heating the three-end hydrogen-based polysiloxane and 2- (hydroxymethyl) phenylboronic acid cyclic monoester ethylene to 60 ℃ for 4 hours in a solvent for 4 hours, adding 3.02g of tannic acid and 4 '-dihydroxybenzene to the mixed solution under the conditions of 4, namely 4-5 g of bisphenol, 4-3, 4' -bis (4 g of boric acid) and 4, 4-methyl) under the conditions of stirring and stirring to obtain a mixed solution, and stirring the mixed solution, and carrying out dynamic modification reaction to the solution.

Example 21

Taking a certain amount of modified polynorbornene (vinyl boron bromoalkane and cyclopentadiene are used as raw materials, boric acid modified norbornene is prepared through Diels-Alder reaction, vinylamine and ethoxycarbonyl isocyanate are reacted, amido modified norbornene is prepared through Diels-Alder reaction with cyclopentadiene, the boron bromoalkane modified norbornene, the amido modified norbornene and norbornene are prepared through addition polymerization by taking metallocene catalyst/methylaluminoxane as a catalytic system, the final product is prepared by heating and dissolving in o-dichlorobenzene solvent to prepare 0.1mol/L solution, 60mL of solution is taken from the solution and added into a No. 1 reactor, and a small amount of deionized water and acetic acid are added dropwise for uniform stirring for later use. Slowly adding 8.3g of polyvinyl alcohol and 1.45g of 1,3, 5-hydroxy-1, 3, 5-trisilicon cyclohexane into a No. 1 reactor, raising the temperature to 80 ℃, stirring and reacting for 30min, then adding 2mL of triethylamine, continuing to react for 4h at 80 ℃, pouring the reaction solution into a proper mold, placing the mold in a vacuum oven at 60 ℃ for further reaction and drying, cooling to room temperature and placing for 30min, and finally obtaining a gelatinous polymer material, wherein a sample has good elasticity and toughness and can be stretched in a large range. The dumbbell type sample is manufactured into dumbbell type sample bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 10mm/min, the tensile strength of the sample is 4.67+/-0.58 MPa, the elongation at break is 538+/-86%, the organic silicon borate ester bonds, the organic boric acid ring ester bonds and the hydrogen bonds are dissociated step by step, the performance of gradually dissipating energy of the material is realized, and the material has higher strength and elongation. After cutting the polymer material, placing the polymer material in a mould at 60 ℃ and applying pressure for 1-2 hours, and then reforming, wherein the performance of the molded sample reaches 91% of that of the original sample. In addition, the prepared product has good plasticity, can be placed in moulds with different shapes according to actual needs, and can be slightly stressed at a certain temperature, so that polymer products with different shapes can be formed according to the moulds. In this embodiment, the polymer may be used as a resilient gasket or impact pad.

Example 22

Adding 32g of acrylate copolymer (1-aminoethylboronic acid pinacol ester reacts with acryloyl chloride to prepare a borate acrylate monomer 1, isocyanate ethyl acrylate reacts with ethylamine to prepare an acrylate monomer 2 containing urea bonds, AIBN is taken as an initiator, the acrylate monomer 1 and methyl acrylate are subjected to emulsion polymerization), 100mL of acetone solvent is heated to 50 ℃ to be stirred and dissolved, 10mL of deionized water is added to be dropwise added, a little acetic acid is slowly added, 21g of silane grafted modified polyvinyl alcohol (taking polyvinyl alcohol as a raw material, reacting the polyvinyl alcohol with acryloyl chloride to obtain a copolymer with double bonds in side chains, then carrying out a thio-ene click reaction on the copolymer with mercaptomethyl diethoxysilane, hydrolyzing the product to prepare 2g of carbon fiber and 3.6g of 3- (hydroxymethyl) -1-adamantanol, stirring, mixing and dispersing for 6h, and continuing stirring and mixing for 3h at 80 ℃. The solvent is removed by vacuum filtration to obtain a residue, and the residue is purified to obtain a dynamic polymer solid, and the product has good strength and toughness. After the polymer material is crushed, the polymer material is placed in a die at 60 ℃ and subjected to pressure for 1-2 hours, and then the polymer material can be reshaped, and the property of the reshaped sample reaches 90% of that of the original sample. The pen holder can be manufactured into a pen holder or pen container with self-repairing characteristic for use.

Example 23

7g of an organoboron compound (prepared by taking magnesium salt of 4-hydroxybutyrate and 1, 8-octanediisocyanate as raw materials for reaction) is added into a No. 1 reactor, 200mL of THF solvent is added, the solution is heated to 60 ℃ for stirring and dissolution, then a small amount of 20% aqueous acetic acid solution is dropwise added, the solution is heated to 60 ℃, 10g of vinylpyrrolidone-silane copolymer (prepared by taking 2-acrylic acid-3- (diethoxymethylsilane) propyl ester as raw materials, AIBN as an initiator, and the product is prepared by free radical polymerization and hydrolysis of the product) and 5g of boric acid modified polynorbornene (prepared by taking vinylboric acid and cyclopentadiene as raw materials and preparing boric acid modified norbornene by Diels-Alder reaction, the boric acid modified norbornene and norbornene are prepared by taking metallocene catalyst/methylaluminoxane as a catalytic system, a small amount of triethylamine is dropwise added under stirring, and the solution is placed in a water bath at 60 ℃ for heating and reaction for 2 hours. Pouring the viscous polymer solution into a proper mold, placing the mold in a vacuum oven at 80 ℃ for drying for 24 hours, cooling to room temperature, and placing for 30 minutes to finally obtain a gelatinous polymer material, wherein the sample has good elasticity and toughness and can be stretched in a large range. The dumbbell type sample is manufactured into dumbbell type sample bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 10mm/min, the tensile strength of the sample is 0.86+/-0.15 MPa, the elongation at break is 685+/-77%, the organic silicon borate bonds, the organic boric anhydride bonds and the hydrogen bonds are dissociated step by step, the performance of gradually dissipating energy of the material is realized, and the material has higher strength and elongation. After cutting the polymer material, placing the polymer material in a mould at 60 ℃ and applying pressure for 1-1.5h, and then reforming, wherein the performance of the molded sample reaches 95% of that of the original sample. In addition, the prepared product has good plasticity, can be placed in moulds with different shapes according to actual needs, and can be slightly stressed at a certain temperature, so that polymer products with different shapes can be formed according to the moulds. The dynamic polymer can be used as a sandwich glue with self-repairing as bulletproof glass.

Example 24

24g of borate-ethylene copolymer (prepared by randomly copolymerizing isopropenylboronic acid pinacol ester and ethylene at 80 ℃ by taking AIBN as an initiator), 4g of sorbitol, 7.5g of 1, 8-octanedioic acid, 3g of modified polyethylene glycol, 1.5g of graphene powder and 0.3g of sodium dodecyl benzene sulfonate are added into a No. 1 reactor, stirred for 30min at 60 ℃, then 0.2g of bentonite is added, the mixture is heated to 80 ℃ for stirring and mixing reaction, after 3h of mixing reaction, the viscous polymer solution is poured into a proper mold, placed into a vacuum oven at 80 ℃ for drying for 24h, cooled to room temperature for 30min, finally, the ionic liquid gel polymer sample with graphene dispersed therein is obtained, and after the sample surface is pressed by fingers, the sample can show good elasticity and can be stretched and extended in a large range. The sample was prepared into a dumbbell-shaped specimen with a size of 80.0X10.0X12.0 mm, and was subjected to a tensile test by a tensile tester at a tensile rate of 50mm/min, and the tensile strength of the specimen was 5.23.+ -. 0.45MPa and the elongation at break was 343.+ -. 72%. The polymer sample in this example exhibited good self-repairing properties, and after being cut by a knife, the section was slightly pressed to fit (optionally slightly wet the section during this process) and then placed in a 60 ℃ die for 90min, and the section was allowed to re-adhere. The dynamic polymer sample in the embodiment can be used as a graphene composite intelligent heat conduction material, is favorable for quick repair of internal micro damage under a heating state based on strong heat conduction of graphene. In addition, due to the high conductivity of graphene, the dynamic polymer in the embodiment has different conductivities under different stress states, and the material can be used as a stress sensor.

Example 25

Taking a certain amount of polyol compound (c) (which is prepared by taking tetraallyloxyethane and 3-mercapto-1, 2-propanediol as raw materials, methanol as a solvent and triethylamine as a catalyst through a thiol-olefin click addition reaction) and dissolving the polyol compound (c) in the methanol solvent to prepare a solution of 0.2 mol/L; 14g of an organoboron compound (a) [ prepared by reacting ethyl isocyanate and propylene glycol monoallyl ether as raw materials with allylboronic acid pinacol ester under the action of AIBN by free radical polymerization ], 100mL of a methanol solvent, 30mL of a methanol solution of a polyol compound (c), 10g of hydrogenated hydroxyl-terminated polybutadiene (hydrogenated HTPB, mn=3000) (d), 7g of a silane compound (b) (prepared by condensation reaction of dicyclohexylcarbodiimide and 4-dimethylaminopyridine with adipic acid using 3-aminopropyl methyldimethoxysilane) and 1mL of triethylamine were added into a reactor 1, after stirring uniformly, the mixture was reacted for 3 hours under the protection of nitrogen at 60 ℃, 1.5g of an expandable microsphere foaming agent was added, the mixture was placed into a suitable mold, the mixture was continuously reacted and dried in a vacuum oven at 80 ℃ for 24 hours, and then cooled to room temperature and left for 30 minutes, a sample was taken out of the mold, and foamed and molded by a vulcanizing press, wherein the molding temperature was 140-150 ℃ and the molding time was 10 MPa-15 MPa, and the final dynamic network material was obtained. The dumbbell type sample is manufactured into dumbbell type bars with the size of 80.0x10.0x2.0mm, a tensile testing machine is used for carrying out tensile testing, the tensile rate is 50mm/min, the tensile strength of the sample is 4.53+/-0.46 MPa, the elongation at break is 683+/-68%, the organic boric acid cyclic ester bonds, the organic boric acid monoester bonds, the organic boric acid silicon ester bonds and the progressive dissociation of hydrogen bonds are carried out, the energy dissipation capacity of the material is improved, and the material has good strength and toughness. After the polymer material is crushed, the polymer material is placed in a die at 60 ℃ and applied with pressure for 1-1.5h, and then the polymer material can be reshaped, and the property of the reshaped sample reaches 92% of that of the original sample. The dynamic polymer has good vibration isolation and stress buffering effects, meanwhile, the ductility of a certain degree is maintained, and the prepared polymer material can be applied to manufacturing household electrical appliance insulating products or automobile damping shock absorption products.

Example 26

Taking a certain amount of dendritic organoboron compound (a) (taking 2, 2-dimethoxy-phenyl ethyl ketone (DMPA) as a photoinitiator, ultraviolet light as a light source, preparing mercaptoboric acid from vinylboric acid and 1, 2-ethanedithiol through thiol-olefin click addition reaction, taking DMPA as a photoinitiator, ultraviolet light as a light source, preparing a primary intermediate product from triallylamine and 1, 2-ethanedithiol through thiol-olefin click addition reaction, preparing a secondary intermediate product from triallylamine and the primary intermediate product through thiol-olefin click addition reaction, preparing a tertiary intermediate product from the tertiary intermediate product and 1, 2-ethanedithiol through thiol-olefin click addition reaction, preparing a quaternary intermediate product from the quaternary intermediate product and the final product from the quaternary boric acid and the 1, 2-ethanedithiol through thiol-olefin click addition reaction), dissolving the primary intermediate product into a toluene solvent, and adding 0.2mg of BHT antioxidant; a certain amount of hydroxy-terminated simethicone (b) is taken and dissolved in toluene solvent by heating to prepare 0.2mol/L solution. 30mL of organoboron compound solution, 30mL of silicone oil solution, 16g of organoboric acid modified silicone rubber (d) (prepared by taking methyl mercapto silicone rubber and vinyl boric acid as raw materials and performing a thio-ene click reaction under ultraviolet irradiation, and DMPA as a photoinitiator) are respectively taken, added into a dry and clean reaction bottle, 1mL of triethylamine is added, stirred uniformly, reacted for 4 hours under the protection of nitrogen at 60 ℃, placed in a proper mold, continuously reacted and dried for 24 hours in a vacuum oven at 80 ℃, cooled to room temperature and placed for 30 minutes, a sample is taken out from the mold, and is manufactured into 80.0X10.0X2.0 mm-sized dumbbell-shaped bars, the tensile test is performed by using a tensile testing machine, the tensile strength of the sample is 5.13+/-0.73 MPa, and the breaking elongation rate is 853+/-167%. After the polymer sample is broken, the polymer sample is placed in a mold at 80 ℃ and is applied with certain pressure for bonding for 1h (the section can be slightly wetted in the process), the sample can be bonded and molded again, and the performance of the molded sample reaches 93% of that of the original sample, so that the polymer sample has good dynamic property and self-repairing property. In the practical use process, the elastic rope can be used as a recyclable elastic rope.

Example 27

Weighing a certain amount of acrylamide-borate copolymer (a) (borate acrylamide monomer is prepared by taking 1-aminoethyl diisopropyl borate and acryloyl chloride as raw materials for reaction, and then the borate acrylamide monomer and N, N-dimethylacrylamide are polymerized by free radicals to obtain a final product), and dissolving the final product in deionized water to prepare a solution of 0.4 mol/L; adding 40mL of the solution, 100mL of THF and 2.3g of compound (b) containing silicon hydroxyl/silicon hydroxyl precursor (prepared by taking 3-aminopropyl methyl dimethoxy silane and adipoyl chloride as raw materials) into a No. 1 reactor, stirring and mixing for 30min, adding 2mL of triethylamine and 8.5g of acrylamide-boric acid copolymer (c) (prepared by taking 3-bromopropyl boric acid and allyl amine as raw materials through hydrocarbylating reaction, then carrying out free radical polymerization on the obtained product and N, N-dimethyl acrylamide by taking AIBN as an initiator, and 2.72g of pentaerythritol (e), continuously stirring and reacting for 2h at 60 ℃, adding 2.5g of hollow glass microspheres, 3g of bentonite, 0.5g of stearic acid and 0.5g of oleic acid, heating and stirring uniformly, placing in a 60 ℃ for 24h for drying and further reaction, finally obtaining a solid elastomer with certain elasticity, placing the polymer material in a 60 ℃ for 1-2h of pressure, and then carrying out molding on the obtained product to obtain a sample which can be molded again after the sample is 94%. The material can be used as a light elastic pellet.

Example 28

Taking a certain amount of organic boron compound (e) (taking diethanolamine and methyl acrylate as raw materials to synthesize 3- (bis (2-hydroxyethyl) amino) methyl propionate, then reacting the 3- (bis (2-hydroxyethyl) amino) methyl propionate with trimethylolpropane in a dropwise adding mode under the catalysis of p-toluenesulfonic acid at 115 ℃ to prepare a first intermediate product, then reacting the first intermediate product with 3- (bis (2-hydroxyethyl) amino) methyl propionate to prepare a second intermediate product, blocking by using 3-isocyanatopropylene, and then dissolving the second intermediate product with 4-mercaptobutanoic acid (the 4-bromobutanoic acid is dripped into a hot thiourea ethanol solution, and then heating and refluxing the solution and a potassium hydroxide aqueous solution together to prepare a product), and preparing a final product by a thio-ene click reaction into a solution of 0.2 mol/L; taking a certain amount of silicon hydroxyl grafted modified butyl rubber (b) (taking brominated butyl rubber and mercaptomethyl diethoxy silane as raw materials, taking DMPA as a photoinitiator, preparing a product through thiol-olefin click addition reaction under the condition of ultraviolet irradiation, and hydrolyzing the product to prepare a solution with the concentration of 0.2mol/L in a chloroform solvent); adding 23g of an organic borate end-capped four-arm ester compound (a) (prepared by taking isopropenylboronic acid pinacol ester and pentaerythritol tetra-3-mercaptopropionate as an initiator and triethylamine as a catalyst through a thio-ene click reaction), 200mL of chloroform, 14g of polyethylene glycol copolymer (d) (prepared by taking ethylene glycol, ethylene oxide and 2-methyl-2-propyl [3- (2-ethylene oxide) propyl ] carbamate as raw materials and boron trifluoride diethyl ether as a catalyst through cationic ring-opening polymerization), 15g of polyvinyl alcohol (c), 30mL of a chloroform solution of an organic boron compound (e) and 30mL of a chloroform solution of a silicon hydroxyl grafting modified butyl rubber (b), after stirring uniformly at 80 ℃ for 30min, adding 2mL of triethylamine, 0.2g of titanium white powder, ultramarine, chrome yellow, phthalocyanine blue and soft carbon black mixed powder which are ground in advance, 0.3g of organic bentonite, 0.5g of polydimethylsiloxane, 0.4g of hydroxyethyl cellulose, 0.2g of dibutyltin dilaurate, a trace fluorescent whitening agent KSN, 30mg of light stabilizer 770 and 0.3g of nano silicon dioxide, continuing stirring at 50 ℃ for 4h, stopping the reaction, standing at room temperature for 12h, and then obtaining the organic coating emulsion composed of dynamic polymers, and after the coating is coated on the surface of a substrate and dried, forming the scratch-resistant and strippable regenerated coating.

The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.

Claims

1. A dynamic polymer comprising a combination of dynamic covalent bonds, wherein said dynamic covalent bonds are organoborate linkages;

wherein the dynamic polymer is prepared by the following steps:

methyl isocyanate and N- (2-hydroxyethyl) acrylamide are used as raw materials to react to prepare a carbamate monomer; then taking AIBN as an initiator, and polymerizing acrylamide, 3-acrylamidophenylboronic acid and carbamate monomers through free radicals to obtain an acrylamide-phenylboronic acid-carbamate copolymer; adding 34g of acrylamide-phenylboronic acid-carbamate copolymer and 300mL of deionized water/THF mixed solvent into a reactor, heating to 50 ℃ to stir and dissolve, slowly adding 3.5g 1,1,3,3,5,5,7,7-octamethyl-1, 7-tetrasiloxydiol and 20mL of 0.3mol/L polyglycerol methanol solution, adding 2g of graphene, performing ultrasonic dispersion for 40min, adding 2.5mL of triethylamine, and continuously stirring and reacting for 2h at 50 ℃; then adding 1.2g of sodium dodecyl benzene sulfonate, 0.7g of bentonite, 0.5g of stearic acid and 0.4g of oleic acid, adding 0.4g of organic bentonite, 0.3g of polydimethylsiloxane, 0.2g of dibutyltin dilaurate and 41mg of light stabilizer 770, heating, stirring and mixing uniformly to obtain a viscous gray black liquid; pouring the viscous solution sample into a mould, drying the sample in a 50 ℃ oven for 24 hours to remove the solvent, cooling to room temperature and standing for 30 minutes to obtain the dynamic polymer.