CN107805308A

CN107805308A - A kind of dynamic aggregation thing and its application with hybrid cross-linked network

Info

Publication number: CN107805308A
Application number: CN201610812775.8A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Tiance Material Technology Co ltd
Priority date: 2016-09-09
Filing date: 2016-09-09
Publication date: 2018-03-16
Anticipated expiration: 2036-09-09
Also published as: CN107805308B

Abstract

The invention discloses a kind of dynamic aggregation thing with hybrid cross-linked network, it includes dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks；Wherein, described dynamic covalent cross-linking is realized by organic boronic estersil key, and dynamic covalent cross-linking reaches more than gel point at least one cross-linked network；Described supermolecule hydrogen bond crosslinks are participated in being formed by the side hydrogen bond group in side base and/or side chain.By dynamic, covalently organic boronic estersil key is combined such dynamic aggregation thing with supermolecule hydrogen bond, by the regulation and control to reaction materil structure, can prepare structure-rich, the various dynamic aggregation thing of performance.The dynamic aggregation thing can be used for making damping, buffering material, defense of resistance to impact material, self-repair material, toughness material etc..

Description

Dynamic polymer with hybrid cross-linked network and application thereof

Technical Field

The invention relates to the field of intelligent polymers, in particular to a dynamic polymer with a hybrid cross-linked network, which is formed by dynamic covalent bonds and supermolecule hydrogen bonds.

Background

After the 21 st century, the progress of science and technology and the development of economy put forward higher requirements on polymers and materials thereof, the polymers are continuously developed towards the direction of functionalization, intellectualization and refinement on the basis of basic performance, the polymer materials are also expanded from structural materials to functional materials with the effects of light, electricity, sound, magnetism, biomedicine, bionics, catalysis, material separation, energy conversion and the like, and a series of novel polymer materials with functional effects such as separation materials, biological materials, intelligent materials, energy storage materials, light guide materials, nanometer materials, electronic information materials and the like appear. For the research on the relationship between the polymer structure and the performance, the polymer structure gradually realizes the synthesis on the molecular design level and the preparation of the polymer capable of achieving the expected functions from the macro level to the micro level, from the qualitative level to the quantitative level and from the static level to the dynamic level.

The traditional polymer is generally composed of common covalent bonds, and the common covalent bonds have higher bond energy, so that the polymer is endowed with good stability and stress bearing capacity. The dynamic covalent bond is a chemical bond which can generate controllable reversible reaction under a certain condition, is a covalent bond which is more stable and weaker than a non-covalent bond, and can realize the fracture and formation of the dynamic covalent bond by changing the external condition. The incorporation of dynamic covalent bonds into polymers is a viable method for forming novel polymers. The significance of introducing dynamic covalent bonds into the polymer is that the dynamic covalent bonds have the dynamic reversible characteristics of non-covalent interaction in supermolecule chemistry on the basis of common covalent bonds, and simultaneously the defects that the self bond energy of the supermolecule non-covalent interaction is weaker, the stability is poorer and the supermolecule non-covalent interaction is easily influenced by external conditions are overcome. Thus, by introducing dynamic covalent bonds into polymers, it is hoped that polymers with a good balance of properties can be obtained.

In order to obtain a polymer with more stable performance, components such as the polymer and the like can form a three-dimensional network structure by a crosslinking means, so that the performances such as the thermal stability, the mechanical property, the solvent resistance and the like of the polymer are improved, and materials such as an elastomer, a thermosetting plastic and the like with good service performance can be obtained. In the case of crosslinked polymers, they can be generally classified as either chemically crosslinked or physically crosslinked. The chemical crosslinking type polymer is generally formed by common covalent bond crosslinking, and once formed, the chemical crosslinking type polymer is very stable and has relatively excellent mechanical properties; the physical crosslinking type polymer is generally formed by crosslinking through non-covalent interaction, and is characterized by dynamic reversibility and variability of the crosslinking structure and the performance of the polymer. The dynamic covalent bond is used for replacing the common covalent bond for crosslinking, so that on one hand, enough bond energy can be obtained, and on the other hand, dynamics which cannot be achieved by the common covalent bond can be provided. However, the polymer systems crosslinked by dynamic covalent bonds are still rare at present, and the dynamic properties of the existing dynamic covalent bonds are very limited, so that catalysts or external energy (such as heating, light and the like) are often required to be added to accelerate the equilibrium process, so that the construction of the polymer materials crosslinked by dynamic covalent bonds is greatly limited.

Disclosure of Invention

The invention provides a dynamic polymer with a hybrid cross-linking network, which comprises dynamic covalent cross-linking and supermolecule hydrogen bond cross-linking, wherein the dynamic covalent cross-linking is realized by organic borate silicate bonds, and the gel point of the dynamic covalent cross-linking in at least one cross-linking network is more than that of the dynamic covalent cross-linking; the supermolecule hydrogen bond crosslinking is formed by polymer chain side groups, side chains or side hydrogen bond groups on the side chains and the side chains. The dynamic polymer can show excellent dynamic reversibility and can show the functional characteristics of stimulus responsiveness, plasticity, self-repairing property, recyclability, reworkability and the like.

The invention is realized by the following technical scheme:

a dynamic polymer having a hybrid cross-linked network comprising dynamic covalent cross-links and supramolecular hydrogen-bonding cross-links, wherein the dynamic covalent cross-links are effected by organoborate silicone linkages and the dynamic covalent cross-links reach above the gel point of the dynamic covalent cross-links in at least one cross-linked network; the supermolecule hydrogen bond crosslinking is formed by polymer chain side groups, side chains or side hydrogen bond groups on the side chains and the side chains.

In embodiments of the invention, the dynamic polymer may be comprised of one or more crosslinked networks. When the dynamic polymer is composed of only one cross-linked network, the dynamic covalent cross-linking and supramolecular hydrogen bond cross-linking are included in the cross-linked network structure. When the dynamic polymer is composed of two or more crosslinked networks, it may be composed of two or more crosslinked networks blended with each other, two or more crosslinked networks interpenetrating with each other, two or more crosslinked networks partially interpenetrating with each other, or a combination of the above three crosslinked networks, but the present invention is not limited thereto.

According to a preferred embodiment of the present invention (first network structure), the dynamic polymer contains only one cross-linked network, and the cross-linked network contains both organoborate silicone bond cross-links and supramolecular hydrogen bond cross-links, wherein the organoborate silicone bond cross-links have a degree of cross-linking above the gel point.

According to another preferred embodiment of the present invention (second network structure), the dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only organoborate silicone bond crosslinks and the organoborate silicone bond crosslinks have a degree of crosslinking above the gel point, and the other crosslinked network comprises only supramolecular hydrogen bond crosslinks.

According to still another preferred embodiment of the present invention (third network structure), the dynamic polymer contains two crosslinked networks, wherein one crosslinked network contains both organoborate silicone bond crosslinks and supramolecular hydrogen bond crosslinks and the degree of crosslinking of the organoborate silicone bond crosslinks is above the gel point, and the other crosslinked network contains only organoborate silicone bond crosslinks and the degree of crosslinking of the organoborate silicone bond crosslinks is above the gel point.

In addition, the invention can also have other various hybrid network cross-linked structure embodiments, one embodiment can comprise three or more than three identical or different cross-linked networks, and the same cross-linked network can comprise different dynamic covalent cross-links and/or different supramolecular hydrogen bond cross-links. The degree of crosslinking of any one crosslink of any one network can also be reasonably controlled to achieve the purpose of regulating and controlling the balance structure and dynamic properties. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

In the invention, the organic boric acid silicon ester bond has the following structure:

wherein at least one borosilicate silicone bond (B-O-Si) is formed between the boron atom and the silicon atom; at least one carbon atom in the structure is connected with a boron atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;refers to a linkage to a polymer chain, a crosslink or any other suitable group through which at least one of the boron atom and the silicon atom, respectively, is attached to the crosslinked network.

In an embodiment of the invention, the organoborate silicone linkage is formed by reacting an organoboronate group and/or organoborate group with a silicon hydroxyl group and/or a silicon hydroxyl precursor.

The organic boric acid group refers to a structural unit (B-OH) consisting of a boron atom and a hydroxyl group connected with the boron atom, wherein the boron atom is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond. In the present invention, one hydroxyl group (-OH) in the organic boronic acid group is a functional group.

The organoborate group in the present invention means a structural unit (B-OR, wherein R is a hydrocarbon group mainly composed of carbon and hydrogen atoms OR a silane group mainly composed of silicon and hydrogen atoms, which is bonded to an oxygen atom through a carbon atom OR a silicon atom) consisting of a boron atom, an oxygen atom bonded to the boron atom, and a hydrocarbon group OR a silane group bonded to the oxygen atom, and wherein the boron atom is bonded to at least one carbon atom through a boron-carbon bond and at least one organic group is bonded to the boron atom through the boron-carbon bond. In the present invention, one ester group (-OR) of the organoborate groups is a functional group.

The silicon hydroxyl group in the invention refers to a structural unit (Si-OH) composed of a silicon atom and a hydroxyl group connected with the silicon atom, wherein the silicon hydroxyl group can be an organosilicon 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 to 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 an organic group), preferably an organosilicon hydroxyl group. In the present invention, one hydroxyl group (-OH) of the silicon hydroxyl groups is a functional group.

The silicon hydroxyl precursor in the invention refers to a structural element (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group, wherein X is the group which can be hydrolyzed to obtain the hydroxyl group and can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoxime, alkoxide and the like. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃，Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂Si-ONa. In the present invention, one of the groups (-X) in the silicon hydroxyl precursor, which can be hydrolyzed to obtain a hydroxyl group, is a functional group.

The supramolecular hydrogen bond crosslinking is formed by a supramolecular crosslinking link established by any suitable hydrogen bonding group through a hydrogen bond, and generally is formed by taking hydrogen as a medium between Z and Y through a hydrogen atom which is covalently connected with an atom Z with large electronegativity and an atom Y with large electronegativity and small radius, so that a Z-H … Y form hydrogen bonding link is generated, wherein Z, Y is any suitable atom with large electronegativity and small radius, can be the same element or different elements, can be selected from F, N, O, C, S, Cl, P, Br, I and other atoms, and is preferably F, N, O atoms and is more preferably O, N atoms.

In an embodiment of the present invention, the side hydrogen bond group participating in the formation of supramolecular hydrogen bond cross-linking comprises the following structural components:

preferably at least one of the following structural components:

wherein,refers to a linkage to a polymer chain, crosslink or any other suitable group, including a hydrogen atom. In embodiments of the present invention, the pendant hydrogen bonding groups are more preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, and derivatives of the above.

Wherein, the side hydrogen bond group is a polymeric chain side group with the molecular weight less than 1000Da and/or a hydrogen bond group on a side chain with the molecular weight more than 1000 Da.

In the embodiment of the invention, the dynamic polymer also optionally contains a suitable skeleton hydrogen bond group to participate in hydrogen bonding action, including intermolecular crosslinking, intramolecular cyclization, intermolecular polymerization and the like, so as to enrich the performance and adjustability of the dynamic polymer.

In the present invention, the backbone hydrogen bonding group contains the following structural elements:

preferably at least one of the following structural components:

wherein,refers to the linkage to the backbone, cross-link, of the polymer backbone.

Wherein the backbone hydrogen bonding group is a hydrogen bonding group present on a backbone of a polymer chain, wherein at least a portion of the atoms are part of the chain backbone.

In the embodiment of the invention, the dynamic polymer with the hybrid cross-linking network can simultaneously contain supramolecular hydrogen bond cross-linking formed by the joint participation of a side hydrogen bond group and a skeleton hydrogen bond group.

In the embodiment of the invention, the dynamic polymer can be obtained by using at least the following compounds as raw materials to perform reasonable formula combination reaction:

an organoboron compound (I) containing organoboronic acid groups and/or organoborate groups; a silicon-containing compound (II) containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor; a compound (III) containing both an organoboronic acid group and/or organoboronate group and a silicon hydroxyl group and/or a silicon hydroxyl group precursor; a compound (IV) containing organoborate silicone linkages and other reactive groups; a compound (V) which is free of organoboronic acid groups, organoborate groups, silicon hydroxyl precursor, and organoboronate silicon ester bonds but contains other reactive groups; wherein the organoboron compound (I), the silicon-containing compound (II) and the compound (V) are not separately used as raw materials for preparing the dynamic polymer. These compounds optionally contain the hydrogen bonding groups, or other reactive groups that can continue to react to form hydrogen bonding groups.

The other reactive groups refer to groups that react spontaneously or under conditions of initiator or light, heat, radiation, catalysis, etc. to form common covalent bonds, and suitable groups include, but are not limited to: hydroxyl group, carboxyl group, carbonyl group, acyl group, amide group, acyloxy group, amino group, aldehyde group, sulfonic group, sulfonyl group, mercapto group, alkenyl group, alkynyl group, cyano group, oxazinyl group, oxime group, hydrazine group, guanidino group, halogen group, isocyanate group, acid anhydride group, epoxy group, acrylate group, acrylamide group, maleimide group, succinimide ester group, norbornene group, azo group, azide group, heterocyclic group, triazolinedione, and the like; hydroxyl, amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, acrylamide groups are preferred.

In an embodiment of the present invention, the crosslinked network skeleton chain of the dynamic polymer may be composed of at least one segment selected from the group consisting of an acrylate polymer, an acrylamide polymer, a polyether polymer, a polyester polymer, a polyamide polymer, a polyurethane polymer, and a polyolefin polymer, depending on the main polymer component and the reaction mode thereof.

The invention preferably provides a hybrid cross-linked network dynamic polymer of polyacrylate. The polyacrylate dynamic polymer refers to that the crosslinked network skeleton structure of the dynamic polymer is mainly composed of polymer chain segments containing one or the combination of acrylic groups and acrylate groups.

The invention preferably provides a hybrid cross-linked network dynamic polymer of polyolefins. The dynamic polymer of polyolefin refers to the dynamic polymer of the invention, the cross-linked network skeleton structure of which is mainly composed of saturated or unsaturated olefin polymer chain segments. Wherein, the olefin polymer segment can be selected from any one or combination of any several of the following: polyethylene chain segments, polypropylene chain segments, polyisobutylene chain segments, polystyrene chain segments, polyvinyl chloride chain segments, polyvinylidene chloride chain segments, polyvinyl fluoride chain segments, polytetrafluoroethylene chain segments, polychlorotrifluoroethylene chain segments, polyvinyl acetate chain segments, polyvinyl alkyl ether chain segments, polybutadiene chain segments, polyisoprene chain segments, polychloroprene chain segments, polynorbornene chain segments and the like.

The invention preferably provides a hybrid cross-linked network dynamic polymer of polyurethanes. The polyurethane dynamic polymer refers to the crosslinked network skeleton structure of the dynamic polymer in the invention, which is mainly composed of polymer chain segments containing one or the combination of carbamate groups, urea groups and thiocarbamate groups.

In embodiments of the present invention, the dynamic polymer morphology of the hybrid cross-linked network may be solution, emulsion, paste, common solid, gel (including hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel, ionic liquid swollen gel), foam, and the like.

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

In the embodiment of the invention, the dynamic polymer has wide adjustable performance range and wide application prospect, and has remarkable application effect in the fields of military aerospace equipment, functional coatings, biomedicine, biomedical materials, energy sources, buildings, bionics, intelligent materials and the like. In particular, the material can be applied to the manufacture of products such as shock absorbers, buffer materials, impact-resistant protective materials, motion protective products, military police protective products, self-repairable coatings, self-repairable plates, self-repairable adhesives, bulletproof glass interlayer glue, tough materials, shape memory materials, sealing elements, toys and the like.

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

(1) the organic boric acid silicon ester bond crosslinking and the supermolecule hydrogen bond crosslinking based on the side hydrogen bond group are combined in the dynamic polymer hybridization crosslinking network structure, and the advantages of crosslinking actions are fully utilized and combined. Wherein, the dynamic covalent organic boric acid silicon ester bond crosslinking provides a covalent dynamic network structure which can change spontaneously or reversibly under the external action for the dynamic polymer, and the supermolecule hydrogen bond crosslinking provides an orthogonal action with the dynamic covalent organic boric acid silicon ester bond crosslinking for the dynamic polymer. Conventional crosslinked structures have limited elongation during stretching due to conventional covalent bonds that are limited by stable crosslinking points, and the polymer will permanently fail once the covalent bonds are broken. In the dynamic polymer, the dynamic covalent organic boric acid silicon ester bonds and the supermolecule hydrogen bonds can be broken in a mode of 'sacrificial bonds' under the action of external force, so that on one hand, a large amount of energy can be dissipated, and excellent tensile toughness and tear resistance can be provided for the crosslinked polymer in a specific structure; on the other hand, super stretching elongation can be obtained; in addition, self-repairability, moldability, reworkability can be obtained.

(2) Due to the nature of the covalent bond of the organic boric acid silicon ester bond, the strength of the organic boric acid silicon ester bond is usually higher than that of the hydrogen bond, when the organic boric acid silicon ester bond is damaged by external force, the order change can be generated between the hydrogen bond crosslinking and the organic boric acid silicon ester bond crosslinking, and the hydrogen bond crosslinking is generally dissociated firstly, so that the gradual dissipation of the force is generated, and the improvement of the tolerance of the material to the external force is facilitated. In addition, because the organic boron silicate ester bond in at least one crosslinking network reaches above the gel point, when the organic boron silicate ester bond is impacted by a quick external force, the organic boron silicate ester bond crosslinking can endow the dynamic polymer with quick viscosity-elasticity transformation, so that the material is easy to obtain a balanced structure in an impacted state, namely a covalent crosslinking solid state, the impact force is dispersed, and the impact injury is reduced.

(3) The dynamic polymer has rich structure and various performances, and the dynamic covalent component and the supermolecular component contained in the polymer have controllability. Particularly, the use of side hydrogen bond groups can obtain hydrogen bond action with adjustable strength, dynamic property and responsiveness in a large range, and provide additional crosslinking for dynamic polymers; meanwhile, the number of introduced side hydrogen bonds and the linking structure of the side hydrogen bonds and a polymer chain can be conveniently regulated and controlled, so that the dynamic polymer with controllable hydrogen bond crosslinking degree and glass transition temperature can be obtained.

(4) The dynamic reactivity of the dynamic reversible bond in the dynamic polymer is strong, and the dynamic reaction condition is mild. Compared with other existing dynamic covalent systems, the organic boric acid silicone ester bond has good thermal stability and high dynamic reversibility, synthesis and dynamic reversibility of dynamic polymers can be realized under the conditions of no need of catalysts, no need of high temperature, illumination or specific pH, preparation efficiency is improved, limitation of use environment is reduced, and application range of the polymers is expanded. In addition, by selectively controlling other conditions (such as adding auxiliary agents, adjusting reaction temperature, etc.), the dynamic covalent chemical equilibrium can be accelerated or quenched to be in a desired state under a proper environment, which is difficult to achieve in the existing supramolecular chemistry and dynamic covalent system.

Detailed Description

The invention relates to a dynamic polymer with a hybrid cross-linking network, which comprises dynamic covalent cross-linking and supermolecule hydrogen bond cross-linking, wherein the dynamic covalent cross-linking is realized by organic borate silicone bonds, and the gel point of the dynamic covalent cross-linking in at least one cross-linking network is more than that of the dynamic covalent cross-linking; the supermolecule hydrogen bond crosslinking is formed by polymer chain side groups, side chains or side hydrogen bond groups on the side chains and the side chains.

In the invention, the organic boric acid silicon ester bond and the supermolecule hydrogen bond exist as a polymerization linkage point and/or a crosslinking linkage point of the dynamic polymer, and are necessary conditions for forming or maintaining a dynamic polymer structure; once the organic boric acid silicon ester bonds and the supermolecule hydrogen bonds contained in the dynamic polymer are dissociated, the polymer system can be decomposed into any one or more units of the following units: monomers, non-crosslinked polymer chain units (including linear polymer segments, branched polymer chain segments, cyclic polymer chain segments, etc.), polymer cluster units (including two-dimensional or three-dimensional clusters, etc.), and the like; meanwhile, the mutual transformation and dynamic reversibility between the dynamic polymer and the units can be realized through the bonding and the dissociation of the organic boric acid silicon ester bonds and the hydrogen bonds, and once the organic boric acid silicon ester bonds are completely or partially regenerated, at least one dynamic covalent crosslinking network with the dynamic covalent crosslinking reaching above the gel point can be obtained.

The term "polymerization" as used in the present invention is a chain extension process/action, and mainly refers to a process in which a reactant of lower molecular weight synthesizes a product of higher molecular weight through a polycondensation, addition polymerization, ring-opening polymerization, or the like. The reactant is generally a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. The product resulting from the polymerization of two or more reactants is referred to as a copolymer. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process of a reactant molecular chain, a branching process of a reactant molecular chain, a ring formation process of a reactant molecular chain, but does not include a crosslinking process of a reactant molecular chain; that is, the "polymerization" refers to a process of polymerization propagation of molecular chains of reactants other than the process of the crosslinking reaction. In embodiments of the invention, "polymerization" also encompasses chain growth by supramolecular hydrogen bonding.

The term "cross-linking" as used in the present invention refers mainly to the process of chemical and/or supramolecular chemical ligation between and/or within reactant molecules by dynamic covalent and/or hydrogen bonds to form products having a two-dimensional, three-dimensional cluster type and/or three-dimensional infinite network type. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Unless otherwise specified, the crosslinking in the present invention includes formation of a three-dimensional infinite network structure above the gel point (including the gel point) and a two-dimensional, three-dimensional cluster structure below the gel point.

The "gel point" in the present invention means a reaction point at which the viscosity of the reactant suddenly increases during the crosslinking process and gelation starts to occur, and the initial crosslinking starts to reach a three-dimensional infinite network, and is also referred to as a percolation threshold. The cross-linked 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 relatively stable and firm; the crosslinked product below the gel point, which is only a loose linked structure and does not form a three-dimensional infinite network structure, has only a small amount of two-dimensional or three-dimensional network structure locally, and does not belong to a crosslinked network that can constitute a whole across the entire polymer structure. In the present invention, unless otherwise specified, crosslinking includes a three-dimensional infinite network including gel points or more (including gel points) and a two-dimensional or three-dimensional cluster structure including gel points or less, and non-crosslinking refers to a polymer chain structure having a degree of crosslinking of zero.

The term "common covalent bond" as used herein refers to a covalent bond in the conventional sense excluding dynamic covalent bond, which is an interaction between atoms via a pair of common electrons, and is difficult to break at normal temperature (generally not higher than 100 ℃) and normal time (generally less than 1 day), and includes, but is not limited to, normal carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc. As used herein, the term "dynamic covalent bond" refers to a specific type of covalent bond that can reversibly cleave and form under appropriate conditions, and in the present invention specifically refers to organoboronate silicone linkages.

According to an embodiment of the present invention, the dynamic polymer in the present invention has a "hybrid cross-linked network" structure, since the dynamic polymer cross-linked network contains both the organoboronate silicate based dynamic covalent cross-links and the supramolecular hydrogen bond cross-links.

In embodiments of the invention, the dynamic polymer may be comprised of one or more crosslinked networks. When the dynamic polymer is composed of only one cross-linked network, the dynamic covalent cross-linking and supramolecular hydrogen bond cross-linking are included in the cross-linked network structure. When the dynamic polymer is composed of two or more crosslinked networks, it may be composed of two or more crosslinked networks blended with each other, or may be composed of two or more crosslinked networks interpenetrating with each other, or may be composed of two or more crosslinked networks partially interpenetrating with each other, or may be composed of a combination of the above three crosslinked networks, but the present invention is not limited thereto; wherein, the two or more cross-linked networks may be the same or different, and may be a combination of partially only dynamic covalent cross-linking and partially only supramolecular hydrogen bonding cross-linking, or a combination of partially only dynamic covalent cross-linking and partially simultaneously dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking, or a combination of partially only supramolecular hydrogen bonding cross-linking and partially simultaneously dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking, or a combination of both dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking in each cross-linked network, but the invention is not limited thereto; the combination must satisfy the condition that the dynamic covalent crosslinking and the supermolecule hydrogen bond crosslinking are simultaneously contained in the dynamic polymer system, and the dynamic covalent crosslinking in at least one crosslinking network reaches above the gel point of the dynamic covalent crosslinking.

For the dynamic polymer of the invention, the dynamic covalent crosslinking reaches above the gel point of the dynamic covalent crosslinking in at least one crosslinking network, and can ensure that even under the condition of only one crosslinking network, the polymer can keep an equilibrium structure as long as the organic boron acid silicon ester bond does not generate dynamic transformation when all the supermolecule hydrogen bonds are dissociated. When two or more crosslinked networks are present, there may be interactions between the different crosslinked networks (including the dynamic covalent organoborate silicon linkages and/or supramolecular hydrogen bonding interactions), or they may be independent of each other; in addition to the fact that the dynamic covalent crosslinking of at least one crosslinked network must be above the gel point of the dynamic covalent crosslinking, the crosslinking of other crosslinked networks (including dynamic covalent crosslinking, supramolecular hydrogen-bonding crosslinking and the sum thereof) may be above the gel point, below the gel point, preferably above the gel point. When the organic borate silicon ester bond cross-linking reaches the gel point or above, the organic borate silicon ester bond cross-linking material can be used as a stress/strain responsive material to better reflect the advantages of the dynamic property, such as the transformation of viscous liquid and elastic solid when the shear thickening property is generated.

In an embodiment of the present invention, the crosslinked network structure of the dynamic polymer may be blended and/or interpenetrated with one or more other non-crosslinked polymer chains, i.e., there is no crosslinking between these polymer chains and the crosslinked network.

According to a preferred embodiment of the present invention (first network structure), the dynamic polymer contains only one cross-linked network, and the cross-linked network contains both organoborate silicone bond cross-links and supramolecular hydrogen bond cross-links, wherein the organoborate silicone bond cross-links have a degree of cross-linking above the gel point. For this embodiment, which contains only one crosslinked network, it is convenient to manufacture.

According to another preferred embodiment of the present invention (second network structure), the dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only organoborate silicone bond crosslinks and the organoborate silicone bond crosslinks have a degree of crosslinking above the gel point, and the other crosslinked network comprises only supramolecular hydrogen bond crosslinks. In the embodiment, the supermolecule hydrogen bond crosslinking network can be dispersed in the organic boric acid silicon bond crosslinking network, and the two networks can be mutually independent in raw material composition, so that the preparation has special advantages.

According to still another preferred embodiment of the present invention (third network structure), the dynamic polymer contains two crosslinked networks, wherein one crosslinked network contains both organoborate silicone bond crosslinks and supramolecular hydrogen bond crosslinks and the degree of crosslinking of the organoborate silicone bond crosslinks is above the gel point, and the other crosslinked network contains only organoborate silicone bond crosslinks and the degree of crosslinking of the organoborate silicone bond crosslinks is above the gel point. In the embodiment, because the organic boron silicate crosslinked network contains two organic boron silicate crosslinked networks, the purpose of reasonably regulating and controlling the balance structure and the mechanical property of the dynamic polymer can be achieved by controlling the structure of the two organic boron silicate crosslinked networks. In this embodiment, once the organoboronate silicon linkages in the two networks are interchanged, the first network structure will be formed.

In an embodiment of the invention, the dynamic covalent crosslinking is effected by organoborate silicone linkages, meaning that the organoborate silicone linkages are contained in the polymer backbone and/or crosslinking linkages of the covalently crosslinked network backbone. The dynamic covalent organoborate silicone linkages may be present on pendant groups and/or side chains of the hybrid cross-linked network backbone chains and further pendant groups and/or side chains thereof, in addition to being present as dynamic covalent crosslinks on the polymer backbone chains of the dynamic polymer hybrid cross-linked network. Wherein only organoborate silicone linkages on the hybrid cross-linking network backbone can form dynamic covalent crosslinks. The organic boric acid silicon ester bond can be reversibly broken and regenerated under the normal condition; under appropriate conditions, the organoboronate silicon ester bond at any position in the dynamic polymer can participate in dynamic reversible exchange. In the hybrid cross-linked network structure of the dynamic polymer, once the organoborate silicone linkages that make up the dynamic covalent cross-linking are dissociated, the overall effective cross-linking degree of the polymer system will decrease. The number of organoboronate silicone linkages on the backbone (in proportion to all linkages) between any two crosslinking sites containing organoboronate silicone linkages is not limited and may be one or more, preferably contains only one. When only one is contained, the dynamic polymer structure is more regular, and the dynamic property is more controllable.

In an embodiment of the present invention, the supramolecular hydrogen bonding crosslinks consist of hydrogen bonds formed between hydrogen bonding groups present at any one or more of polymer backbone chains, side groups, side chains, branched chains, terminal groups, and non-crosslinked polymer backbone chains, side groups, side chains, branched chains, terminal groups of the dynamic polymer hybrid crosslinked network. Wherein said hydrogen bonding groups may also be present in small molecules.

Wherein, the 'hybrid cross-linked network polymer skeleton chain' refers to any chain segment existing in the cross-linked network skeleton, and comprises a main chain and cross-linked links on a cross-linked cluster and/or an infinite three-dimensional network skeleton; herein, the cross-linked chain between the polymer chains may be an atom, a single bond, a group, a segment, a cluster, etc., and thus the cross-linked chain skeleton between the polymer chains is also regarded as a polymer skeleton chain. Wherein, the side chain refers to a chain structure which is connected with a polymer skeleton chain in a hybrid cross-linked network structure and a non-cross-linked polymer structure and is distributed beside the skeleton chain and has a molecular weight of more than 1000 Da; wherein the "branched chain" or "branching chain" refers to a chain structure branching from a polymer backbone chain or any other chain and having a molecular weight of more than 1000 Da; for simplicity, the side chains, branches, and branched chains in the hybrid crosslinked network structure and in the non-crosslinked polymer structure of the present invention are collectively referred to as side chains unless otherwise specified. Wherein, the side group refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with a polymer skeleton chain and distributed beside the skeleton chain in a hybrid crosslinking network structure and a non-crosslinking polymer structure. For "side chains" and "side groups", it may have a multi-step structure, i.e. the side chain may continue to have side groups and side chains, and the side chain of the side chain may continue to have side groups and side chains, wherein the side chain also includes branched and forked chains, etc. chain structures. Wherein, the "terminal group" refers to a chemical group which is connected with the polymer skeleton chain and/or the side chain in the hybrid cross-linked network structure and the non-cross-linked polymer structure and is positioned at the terminal of the skeleton chain and/or the side chain; in the present invention, the side groups may have terminal groups in specific cases. In the non-crosslinked polymer, the backbone chain is the main chain. For hyperbranched and dendritic chains and their related chain structures, the polymer chains can be considered as branches or as backbones.

In an embodiment of the invention, the organoborate silicone linkage is formed by reacting an organoboronate group and/or organoborate group with a silicon hydroxyl group and/or a silicon hydroxyl precursor. Where any suitable organoboronate group and/or organoboronate group may be used in combination with the silicon hydroxyl group and/or silicon hydroxyl group precursor to form the organoboronate silicone bond, preferably the organoboronate group is used in combination with the silicon hydroxyl group, the organoboronate group is used in combination with the silicon hydroxyl group precursor, the organoboronate group is used in combination with the silicon hydroxyl group to form the organoboronate silicone bond, more preferably the organoboronate group is used in combination with the silicon hydroxyl group, and more preferably the organoboronate group is used in combination with the silicon hydroxyl group to form the organoboronate silicone bond.

The silicon hydroxyl precursor in the present invention means a precursor composed of a silicon atom and one bonded to the silicon atomStructural unit (Si-X) composed of groups which are hydrolyzed to obtain hydroxyl, wherein X is a group which is hydrolyzed to obtain hydroxyl and can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoxime, alkoxide and the like. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃，Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂Si-ONa. In the present invention, one of the groups (-X) in the silicon hydroxyl precursor, which can be hydrolyzed to obtain a hydroxyl group, is a functional group.

The functional groups mentioned in the present invention, unless otherwise specified, refer to the above-mentioned hydroxyl group in the organoboronate group, ester group in the organoboronate group, hydroxyl group in the silicon hydroxyl group, and a group in the silicon hydroxyl group precursor which can be hydrolyzed to give a hydroxyl group.

In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.

The bonding of the monodentate, bidentate and tridentate hydrogen bonds 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 crosslinking is weak, and the dynamic polymer can play a role in promoting the dynamic polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, the dynamic property of hydrogen bond crosslinking is strong, and the dynamic property, such as self-repairability, energy absorption characteristic and the like, can be provided together with the dynamic covalent organic boric acid silicon ester bond. In embodiments of the invention, it is preferred that no more than four teeth are hydrogen bonded.

In an embodiment of the present invention, the side hydrogen bonding groups participating in the formation of supramolecular hydrogen bonding cross-linking refer to hydrogen bonding groups on side groups of polymeric chains, side chains (including branched and forked chains) having a molecular weight of not more than 1000Da, wherein the hydrogen bonding groups may also be present on a multilevel structure of side groups and/or side chains, which comprises the following structural components:

preferably at least one of the following structural components:

Examples of suitable pendant and/or pendant hydrogen bonding groups on side chains (including branched and forked chains) are, but not limited to:

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

Pendant hydrogen bonding groups have structural diversity including, but not limited to, hydrogen bonding donor and acceptor numbers, group size, length and rigidity of the linkage to the polymer chain; in addition, the number of pendant hydrogen bonding groups attached to the polymer chain is also widely adjustable. The side hydrogen bond groups participate in the formation of hydrogen bond crosslinking, so that the supermolecule hydrogen bond crosslinking with large-range adjustable strength, dynamic property, responsiveness and crosslinking density can be obtained, and meanwhile, the dynamic property of the hydrogen bond, the glass transition temperature of the crosslinked polymer and the like can be controlled through the regulation and control of the chain linking with the polymer, so that various dynamic properties of the dynamic polymer can be effectively regulated and controlled.

In the present invention, the backbone hydrogen bonding group refers to a hydrogen bonding group present on the backbone of a polymer chain, wherein at least a portion of the atoms are part of the chain backbone, which contains the following structural elements:

preferably at least one of the following structural components:

Suitable backbone hydrogen bonding groups on the hybrid cross-linked network backbone and the non-cross-linked chain backbone are exemplified by (but the invention is not limited to):

in the invention, the same dynamic polymer may contain one or more than one hydrogen bonding group, and the same cross-linking network may also contain one or more than one hydrogen bonding group, that is, the dynamic polymer may contain one hydrogen bonding group or a combination of a plurality of hydrogen bonding groups. The hydrogen bonding groups may be formed by any suitable chemical reaction, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reaction between the succinimide ester group and amino, hydroxyl, sulfhydryl groups.

In the present invention, the supramolecular hydrogen bond crosslinks in the crosslinked network may have any suitable degree of crosslinking, either above or below their gel point. The supramolecular hydrogen bond crosslinks may be generated during dynamic covalent crosslinking of dynamic polymers; or the dynamic covalent crosslinking is carried out after the supermolecule hydrogen bond crosslinking is generated in advance; it is also possible, but not limited to, to generate supramolecular hydrogen bonding crosslinks during subsequent formation of the dynamic polymer after formation of the dynamic covalent crosslinks.

an organoboron compound (I) containing organoboronic acid groups and/or organoborate groups; a silicon-containing compound (II) containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor; a compound (III) containing both an organoboronic acid group and/or organoboronate group and a silicon hydroxyl group and/or a silicon hydroxyl group precursor; a compound (IV) containing organoborate silicone linkages and other reactive groups; a compound (V) which is free of organoboronic acid groups, organoborate groups, silicon hydroxyl precursor, and organoboronate silicon ester bonds but contains other reactive groups; wherein the organoboron compound (I), the silicon-containing compound (II) and the compound (V) are not separately used as raw materials for preparing the dynamic polymer. The compounds optionally contain the hydrogen bonding groups, or optionally contain other reactive groups that can continue to react to form hydrogen bonding groups.

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

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

The organoboron compound (I) containing an organoboronate group and/or organoboronate group described in the present invention can be represented by the following structure:

wherein A is a module containing an organic boric acid group and/or an organic boric acid ester group; m is the number of the modules A, and m is more than or equal to 1; l is a substituent group on a single module A, or a linking group between two or more modules A; p is the number of groups L, and p is more than or equal to 1.

The module A containing the organic boric acid group can be selected from any one or any several structures as follows:

wherein, K₁Is a group directly attached to the boron atom and selected from any 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; the ring structure in A4 is a non-aromatic or aromatic boron heterocyclic group containing at least one organic boric acid group, the boron atom is placed in the ring structure, the ring structure can be a small molecular ring or a macromolecular ring, and the ring structure is preferably a 3-100-membered ring, more preferably a 3-50-membered ring, more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic structure in A4 are each independently a carbon atom, a boron atom or other hetero atom, 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 bonded to the group L; the hydrogen atoms on the respective ring-forming atoms of the cyclic structure in a4 may or may not be substituted; the cyclic structure in A4 can be a single-ring structure, a multi-ring structure, a spiro ring structure, a fused ring structure, a bridged ring structure or a nested ring structure;represents a linkage to the group L; the boron atoms in the various structures are linked to at least one carbon atom by a boron-carbon bond, and at least one organic group is linked to the boron atom by the boron-carbon bond.

The organoborate group-containing module A can be selected from any one or any several of the following structures:

wherein, K₂Is a group directly attached to the boron atom,it is 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; r₁、R₂、R₃、R₄、R₆Is a monovalent organic group or a monovalent organosilicon group directly bonded to an oxygen atom through a carbon atom or a silicon atom, selected from any of the following structures: 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 greater than 1000 Da; r₅Is a divalent organic or divalent organosilicon group directly attached to two oxygen atoms, directly attached to the oxygen atoms through a carbon or silicon atom, selected from any of the following structures: a divalent small molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent small molecule silane group having a molecular weight of no more than 1000Da, and a divalent polymer chain residue having a molecular weight greater than 1000 Da; the ring structure in B5 is a non-aromatic or aromatic boron heterocyclic group containing at least one organoboronate group, the boron atom is placed in the ring structure, the ring structure can be a small molecular ring or a macromolecular ring, and the ring structure is preferably a 3-100-membered ring, more preferably a 3-50-membered ring, more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic structure in B5 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 organoborate group, and at least one ring-forming atom is linked to the group L; the hydrogen atoms on the respective ring-forming atoms of the cyclic structure in B5 may or may not be substituted; the ring structure in B5 can be a single ring structure, a multi-ring structure, a spiro ring structure, a fused ring structure, a bridged ring structure or a nested ring structure;represents a linkage to the group L; the boron atoms in the various structures are linked to at least one carbon atom by a boron-carbon bond, and at least one organic group is linked to the boron atom by the boron-carbon bond.

In the present invention, in the module a containing an organic boronic acid group and/or an organic boronic acid ester group, a boron atom may be simultaneously connected with a hydroxyl group and an ester group, and the same module may also simultaneously contain at least one boronic hydroxyl group and at least one boronic acid ester group, for example:

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

In the present invention, when the block A containing an organoboronic acid group and/or organoboronate group is present in a polymer and there are two or more of the linkages, it may be linked to a polymer chain that is not cyclic or clustered, or to cyclic or clustered side groups/side chains; when there is only one such linkage, it may be attached at any position of the polymer chain.

When m is 1, p is 1 or 2, and L is a substituent on the single module a; when p ═ 2, L can be selected from the same structure or a plurality of different structures; the structure of the L can be selected from any one or more of the following: small hydrocarbon groups with molecular weight not exceeding 1000Da, and polymer chain residues with molecular weight greater than 1000 Da.

When m is greater than 1, the modules A can be selected from the same structure or a plurality of different structures, wherein p is more than or equal to 1, and L is a connecting group between two or more modules A; when p is more than or equal to 2, L can be selected from the same structure or a plurality of different structures; the structure of the L can be selected from any one or more of the following: single bonds, heteroatom linkers, divalent or polyvalent small molecule hydrocarbyl groups having a molecular weight of no more than 1000Da, and divalent or polyvalent polymer chain residues having a molecular weight greater than 1000 Da.

The silicon-containing compound (II) containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor described in the present invention may be an organic silicon-containing compound or an inorganic silicon-containing compound, which may be represented by the following structure:

wherein G is a module containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor; n is the number of the modules G, and n is more than or equal to 1; j is a substituent group on a single module G, or a linking group between two or more modules G; q is the number of the groups J, and q is more than or equal to 1.

The module G containing the silicon hydroxyl can be selected from any one or any several structures of the following:

wherein, K₃、K₄、K₅、K₆、K₇Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbyl with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da, and inorganic macromolecular chain residues with the molecular weight more than 1000 Da; wherein, the cyclic structure in C7, C8 and C9 is a non-aromatic or aromatic silicon heterocyclic group containing at least one silicon hydroxyl group, a silicon atom is arranged in the cyclic structure, the cyclic structure can be a micromolecular ring or a macromolecular ring, and the cyclic structure 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 structure in C7, C8, C9 are each independently a carbon atom, a silicon atom, or other hetero atom, 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 bonded to the group J; the hydrogen atoms on the ring-forming atoms of the cyclic structures in C7, C8, and C9 may or may not be substituted; the cyclic structure in C7, C8 and C9 can be a single-ring structure, a multi-ring structure, a spiro ring structure, a fused ring structure, a bridged ring structure or a nested ring structure;represents a linkage to the group J.

The module G containing the silicon hydroxyl precursor can be selected from any one or any several structures of the following:

wherein, K₈、K₉、K₁₀、K₁₁、K₁₂Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbyl with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da, and inorganic macromolecular chain residues with the molecular weight more than 1000 Da; x₁、X₂、X₃、X₄、X₅、X₆、X₇、X₈、X₉、X₁₀、X₁₁、X₁₂、X₁₃、X₁₄Is a hydrolyzable group directly bonded to the silicon atom, including but not limited to halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide, and the like, preferably halogen, alkoxy; wherein, the ring structure in D7, D8 and D9 is a non-aromatic or aromatic silicon heterocyclic group containing at least one silicon hydroxyl precursor, a silicon atom is arranged in the ring structure, the ring structure can be a micromolecule ring or a macromolecule ring, and the ring structure 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 structure in D7, D8, D9 are each independently a carbon atom, a silicon atom or another hetero atom, and at least one ring-forming atom is a silicon atom and constitutes a silicon hydroxyl group precursor, and at least one ring-forming atom is a silicon atomA group is attached to group J; the hydrogen atoms on the ring-forming atoms of the cyclic structures in D7, D8 and D9 may or may not be substituted; the cyclic structures in D7, D8 and D9 can be single-ring structures, multi-ring structures, spiro structures, fused ring structures, bridge ring structures and nested ring structures;represents a linkage to the group J. It is to be noted that, in the above-mentioned structure, rings may also be formed between the different groups K, between the different groups X, and between the groups K and X, as appropriate.

In the invention, in the module G containing the silicon hydroxyl and/or the silicon hydroxyl precursor, at least one hydroxyl and at least one hydroxyl precursor can be simultaneously connected to one silicon atom, and the same module also can simultaneously contain at least one silicon hydroxyl and at least one silicon hydroxyl precursor. For example:

the compound contains silicon hydroxyl and a silicon hydroxyl precursor, which is beneficial to regulating and controlling the parameters of the solubility, the reaction rate, the reaction degree and the like of the compound and can be used for regulating and controlling the performances of the dynamic polymer such as the dynamic property and the like.

In the present invention, when the module G containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor is present in a polymer and there are two or more of the linkages, it may be linked to a polymer chain that is not cyclic or clustered, or to cyclic or clustered side groups/side chains; when there is only one such linkage, it may be attached at any position of the polymer chain.

When n is 1, q is 1,2 or 3, J is a substituent on the single module G; when q is 2 or 3, J may be selected from the same structure or a plurality of different structures; the J structure can be selected from any one or more of the following: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da and inorganic macromolecular chain residues with the molecular weight more than 1000 Da.

When n is greater than 1, the modules G can be selected from the same structure or a plurality of different structures, wherein q is more than or equal to 1, and J is a connecting group between two or more modules G; when q is more than or equal to 2, J can be selected from the same structure or a plurality of different structures; the J structure can be selected from any one or more of the following: a single bond, a heteroatom linking group, a divalent or polyvalent small molecule alkyl group with the molecular weight not more than 1000Da, a divalent or polyvalent polymer chain residue with the molecular weight more than 1000Da, a divalent or polyvalent inorganic small molecule chain residue with the molecular weight not more than 1000Da, and a divalent or polyvalent inorganic large molecule chain residue with the molecular weight more than 1000 Da.

The compound (III) containing both an organoboronate and/or organoboronate group and a silicon hydroxyl and/or silicon hydroxyl precursor as described in the present invention can be represented by the following structure:

wherein, A is a module containing an organoboronic acid group and/or an organoboronate group, and the specific definition thereof can refer to the definition of the module A in the organoboron compound (I), which is not described herein again, wherein A is preferably a module containing an organoboronate group; x is the number of the modules A, and x is more than or equal to 1; when x is larger than or equal to 2, the module A can be selected from the same structure or a plurality of different structures; g is a module containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor, and the specific definition of G can refer to the definition of module G in the silicon-containing compound (II), which is not described herein again, wherein G is preferably a module containing a silicon hydroxyl group precursor; y is the number of the modules G, and y is more than or equal to 1; when y is more than or equal to 2, the module G can be selected from the same structure or a plurality of different structures; t is a connecting group between two or more A, or between two or more G, or between A and G, and the structure of T can be selected from any one or more of the following: single bonds, heteroatom linkers, divalent or multivalent small molecule hydrocarbyl groups having a molecular weight of no more than 1000Da, and divalent or multivalent polymer chain residues having a molecular weight greater than 1000 Da; v is the number of groups T, and v is more than or equal to 1; when v.gtoreq.2, T can be selected from the same structure or a plurality of different structures.

When the group L in the structure of the organoboron compound (I), the group J in the structure of the silicon-containing compound (II), and the group T in the structure of the compound (III) are selected from chain structures other than cyclic structures, the group A may be bonded to the end of L or may be bonded to any position in L; the group G can be connected to the terminal of J and can also be connected to any position in J; the groups A and G may be attached to the end of T, or may be attached at any position in T.

For the organoboron compound (I), the silicon-containing compound (II) and the compound (III), any one of hydroxyl groups in the organoboron group, any one of ester groups in the organoboron group, any one of hydroxyl groups in the silicon hydroxyl group and any one of groups in the silicon hydroxyl group precursor which can be hydrolyzed to obtain hydroxyl groups are all one functional group. For the organoboron compound (I), the silicon-containing compound (II) may be monofunctional, difunctional, trifunctional or polyfunctional, for example, in the case of the structures

The organic boron compound (I) is respectively a monofunctional group, a bifunctional group, a trifunctional group and a tetrafunctional group; as another example, for a structure of

The silicon-containing compound (II) of (1) is a monofunctional group, a bifunctional group, a trifunctional group or a tetrafunctional group; for compound (III), it may be a difunctional, trifunctional or multifunctional compound, for example, for structures

The compound (III) of (2) is bifunctional, trifunctional, tetrafunctional, or pentafunctional.

The organoboron compound (I), the silicon-containing compound (II) and the compound (III) may optionally contain other reactive groups and may optionally contain hydrogen bonding groups in addition to the organoboronic acid group and/or the organoboronate group, the silicon hydroxy group and/or the silicon hydroxy precursor.

The compound (IV) containing an organoboronate silicone bond and other reactive groups described in the present invention can be represented by the following structure:

wherein E is a module containing an organoborate silicone bond; u is the number of the modules E, and u is more than or equal to 1; y is a substituent group on a single module E, or a substituent group on a single module E and a linking group between two or more modules E, and at least one group Y is linked to a boron atom of an organoboronate silicone bond and at least one group Y is linked to a silicon atom of an organoboronate silicone bond; wherein at least one group Y contains at least one other reactive group, and the number of other reactive groups contained in all groups Y is 2 or more; r is the number of the groups Y, and r is more than or equal to 2.

The organic borate silicon ester bond-containing module E can be represented by the following structure:

wherein, K₁₃、K₁₆、K₂₀Are groups directly attached to the boron atom, each independently selected from any of the following structures: hydrogen atom, hetero atom group, molecular weightA small hydrocarbon group of no more than 1000Da, a polymer chain residue of molecular weight greater than 1000 Da; k₁₄、K₁₅、K₁₇、K₁₈、K₁₉、K₂₁Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbyl with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da, and inorganic macromolecular chain residues with the molecular weight more than 1000 Da;represents a linkage to the group Y. It is to be noted that, in the above structure, rings may also be formed between the different groups K, between the different groups Y, and between the groups K and Y as appropriate; the radical Y may be bonded to the boron atom via a Si-O bond or may be bonded to the silicon atom via a B-O bond.

In the present invention, the module E containing organoboronate silicon ester bond can be obtained by condensation reaction or ester exchange reaction between any one or more of the modules A containing organoboronate and/or organoboronate group and any one or more of the modules G containing silicon hydroxyl group and/or silicon hydroxyl group precursor.

When u is 1, r is 2,3, 4 or 5, Y is a substituent group on a single module E, Y may be selected from the same structure or a plurality of different structures, and the number and structure of the other reactive groups contained in Y must be such that the dynamic polymer can be obtained; the structure of Y can be selected from any one or more of the following: small hydrocarbon groups with molecular weight not exceeding 1000Da, and polymer chain residues with molecular weight greater than 1000 Da.

When u is greater than 1, the module E can be selected from the same structure or a plurality of different structures, wherein r is more than or equal to 2, Y is a substituent group on a single module E and a connecting group between two or more modules E, Y can be selected from the same structure or a plurality of different structures, and the number and the structure of other reactive groups contained in Y must ensure that the dynamic polymer can be obtained; the Y structure can be selected from at least one of a small molecular hydrocarbon group with the molecular weight not more than 1000Da, a polymer chain residue with the molecular weight more than 1000Da, a single bond, a heteroatom linking group, a divalent or polyvalent small molecular hydrocarbon group with the molecular weight not more than 1000Da, and a divalent or polyvalent polymer chain residue with the molecular weight more than 1000 Da.

For compounds (IV) containing organoborate silicone linkages and other reactive groups, these are typically organoborate silicone linkage containing monomers, organoborate silicone linkage containing oligomers, organoborate silicone linkage containing prepolymers. Compound (IV) can be prepared by any suitable method, including by suitable organoboron compounds (I) and silicon containing compounds (II). Preferably, the compound (IV) can be prepared by reacting at least one organoboron compound (I) containing other reactive groups with at least one silicon-containing compound (II) containing other reactive groups, by reacting at least one organoboron compound (I) containing other reactive groups with at least one silicon-containing compound (II) containing no other reactive groups, or by reacting at least one organoboron compound (I) containing no other reactive groups with at least one silicon-containing compound (II) containing other reactive groups; the compound (IV) can also be prepared by reacting at least one compound (III) containing other reactive groups or with an organoboron compound (I) and/or a silicon-containing compound (II).

The structure of the compound (V) in the present invention is not particularly limited, and any suitable compound which does not contain an organoboronic acid group, an organoboronate group, a silylhydroxy precursor, and an organoboronate silyllinkage but contains other reactive groups can be selected as the compound (V) in the present invention.

The heteroatom group mentioned in the present invention may be any suitable heteroatom-containing group, which may be selected from any of the following groups, but the present invention is not limited thereto: halogen, thiol, carboxyl, nitro, primary amine, silicon, phosphorus, triazole, isoxazole, amide, imide, thioamide, enamine, carbonate, thiocarbonate, dithiocarbonate, trithiocarbonate, carbamate, thiocarbamate, dithiocarbamate, thioester, dithioester, orthoester, phosphate, phosphite, phosphinate, phosphoryl, phosphoramidite, hypophosphoryl, thiophosphoryl, thiophosphorous acyl, thiophosphorous phosphinate, phospho, phosphorosilicate, silanoate, carboxamide, thioamide, phosphoramidite, pyrophosphoroamide, cyclophosphamide, ifosfamide, thiophosphoryl, orthosilicic acid, metasilicic acid, silicic acid, boric acid, aconitic acid, or the like, Peptide bonds, acetals, cyclic acetals, mercaptals, azaacetals, azathioacetals, dithioacetals, hemiacetals, thiohemiacetals, azahemiacetals, ketals, thioketals, azaketals, azathioketals, acylhydrazone bonds, oxime bonds, thiooxime ether groups, semicarbazone bonds, thiosemicarbazone bonds, hydrazine groups, hydrazide groups, thiocarbohydrazide groups, azocarbohydrazide groups, thioazocarbonylhydrazide groups, carbazate groups, carbazothioformate groups, carbazazine groups, thiocarbcarbazide groups, azo groups, urea groups, isourea groups, isothiourea groups, allophanate groups, thioallophanate groups, guanidine groups, amidino groups, aminoguanidine groups, amidino groups, imido thioester groups, nitroxyl groups, nitrosyl groups, sulfonic acid ester groups, sulfinic acid ester groups, sulfonamide groups, sulfenamide groups, sulfonyl groups, hydrazino groups, guanido groups, aminogroups, thioketal groups, sulfonylurea groups, maleimides, triazolinediones.

The small-molecule hydrocarbon radicals mentioned in the context of the present invention, which have a molecular weight of not more than 1000Da, generally contain from 1 to 71 carbon atoms and may or may not contain heteroatom groups. In general terms, the small molecule hydrocarbyl group may be selected from any of the following groups, any unsaturated form, any substituted form, any hybridized form, and combinations thereof: c_1-71Alkyl, ring C_3-71Alkyl, phenyl, benzyl, aromatic hydrocarbonsA group; the small-molecule hydrocarbon group is preferably methyl, ethyl, propyl, propylene, butyl, butylene, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl; more preferably methyl, ethyl, propyl, phenyl.

The polymer chain residues having a molecular weight of greater than 1000Da referred to in the present invention may be any suitable polymer chain residues including, but not limited to, carbon chain polymer residues, heterochain polymer residues, elemental organic polymer residues. Wherein, the polymer can be a homopolymer, and also can be a copolymer composed of any several monomers, oligomers or polymers; the polymer chains may be flexible chains or rigid chains.

Wherein the carbon chain polymer residue, which may be any suitable polymer residue having a macromolecular backbone consisting essentially of carbon atoms, may be selected from any of the following groups, any unsaturated form, any substituted form, any hybridized form, and combinations thereof: polyolefin-based chain residues such as 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, polychlorotrifluoroethylene chain residues, polyvinyl acetate chain residues, polyvinyl alkyl ether chain residues, polybutadiene chain residues, polyisoprene chain residues, polychloroprene chain residues, polynorbornene chain residues and the like; polyacrylic chain residues such as polyacrylic chain residues, polyacrylamide chain residues, polymethyl acrylate chain residues, polymethyl methacrylate chain residues, and the like; polyacrylonitrile chain residues such as polyacrylonitrile chain residues and the like; preferably, the polymer is selected from the group consisting of a polyethylene chain residue, a polypropylene chain residue, a polystyrene chain residue, a polyvinyl chloride chain residue, a polybutadiene chain residue, a polyisoprene chain residue, a polypropylene chain residue, a polyacrylamide chain residue, and a polyacrylonitrile chain residue.

The heterochain polymer residue, which may be a polymer residue having a backbone of any suitable macromolecule consisting essentially of carbon atoms and heteroatoms such as nitrogen, oxygen, sulfur, and the like, may be selected from any of the following groups, unsaturated forms of any, substituted forms of any, hybridized forms of any, and combinations thereof: polyether chain residues such as polyoxymethylene chain residues, polyethylene oxide chain residues, polypropylene oxide chain residues, polytetrahydrofuran chain residues, epoxy resin chain residues, phenol resin chain residues, polyphenylene ether chain residues, and the like; polyester chain residues such as polycaprolactone chain residues, polypentanolide chain residues, polylactide chain residues, polyethylene terephthalate chain residues, unsaturated polyester chain residues, alkyd resin chain residues, polycarbonate chain residues, biopolyester chain residues, liquid crystal polyester chain residues and the like; polyamine-based chain residues such as polyamide chain residues, polyimide chain residues, polyurethane chain residues, polyurea chain residues, polythiourethane chain residues, urea-formaldehyde resin chain residues, melamine resin chain residues, liquid crystal polymer chain residues, and the like; polysulfide chain residues such as polysulfone chain residues, polyphenylene sulfide chain residues, polysulfide rubber chain residues, and the like; preferably a polyoxymethylene chain residue, a polyethylene oxide chain residue, a polytetrahydrofuran chain residue, an epoxy resin chain residue, a polycaprolactone chain residue, a polylactide chain residue, a polyamide chain residue, a polyurethane chain residue, a polyurea chain residue; the heterochain polymer residues, which can be formed by click reactions, such as the CuAAC reaction, the thio-ene reaction.

The elemental organic polymer residue may be any suitable polymer residue having a macromolecular backbone consisting essentially of heteroatoms of inorganic elements such as silicon, boron, aluminum, and the like, and heteroatoms of nitrogen, oxygen, sulfur, phosphorus, and the like, selected from any of the following groups, unsaturated forms of any of the following, substituted forms of any of the following, hybridized forms of any of the following, and combinations thereof: silicone-based polymer chain residues such as polyorganosiloxane chain residues, polyorganosiloxane borane chain residues, polyorganosiloxane nitrogen chain residues, polyorganosiloxane sulfane chain residues, polyorganopolysiloxane chain residues; organoboron-based polymer chain residues such as polyorganoborane chain residues, polyorganoboroxane chain residues, polyorganoborazine chain residues, polyorganoborasulfane chain residues, polyorganoboraphosphoalkane chain residues, and the like; an organophosphorus-based polymer chain residue; an organolead-based polymer chain residue; an organotin-based polymer chain residue; an organic arsenic-based polymer chain residue; an organic antimony-based polymer chain residue; preferably polyorganosiloxane chain residues, polyorganoborane chain residues.

The small-molecule silane group with the molecular weight not exceeding 1000Da in the invention can be any suitable small-molecule silane group with the main molecular chain mainly composed of silicon atoms and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and the like, and in general, the small-molecule silane group can be selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and any combination thereof: a silicone chain residue, a siloxane chain residue, a thiosiloxane chain residue, a silazane chain residue; preferred are a silicone chain residue and a siloxane chain residue.

The inorganic small molecular chain residue with the molecular weight not exceeding 1000Da can be the inorganic small molecular chain residue with any suitable molecular main chain and side chain mainly composed of heteroatoms of inorganic elements such as silicon, boron, aluminum and the like and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and the like, and in general, the inorganic small molecular chain residue can be selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and any combination thereof: chain sulfur residue, silane chain residue, silicon oxide chain residue, sulfur nitrogen compound chain residue, phosphazene compound chain residue, phosphorus oxide chain residue, borane chain residue, boron oxide chain residue; preferred are chain sulfur residues, silane chain residues, siloxane compound chain residues, phosphazene compound chain residues, and borane chain residues.

The inorganic macromolecular chain residue having a molecular weight of more than 1000Da mentioned in the present invention may be any suitable inorganic macromolecular chain residue having a macromolecular main chain and side chains mainly composed of heteroatoms of inorganic elements such as silicon, boron, aluminum and the like and heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and the like, and 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 and combinations thereof: chain sulfur polymer residues, polysiloxane chain residues, polysulfide silicon chain residues, polysulfide nitrogen chain residues, polyphosphate chain residues, polyphosphazene chain residues, polychlorophosphazene chain residues, polyborane chain residues, polyboroxine chain residues; or any inorganic macromolecule with residues and residues which is subjected to surface modification in the following group: zeolite-type molecular sieves, aluminum phosphate molecular sieves, zirconium phosphate molecular sieves, heteropolyacid salt molecular sieves, diamond, graphite, graphene oxide, carbon nanotubes, fullerene, carbon fiber, white phosphorus, red phosphorus, phosphorus pentoxide, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talc, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, sulfur nitride, calcium silicide, silicates, glass fiber, beryllium oxide, magnesium oxide, mercury oxide, borohydride, boron nitride, boron carbide, aluminum nitride, diaspore, gibbsite, corundum, titanium dioxide; preferred are chain sulfur polymer residues, polysiloxane chain residues, polyphosphazene chain residues, polyborane chain residues, surface-modified graphene, surface-modified carbon nanotubes, surface-modified carbon fibers, surface-modified silica, surface-modified silicon nitride, surface-modified silicon carbide, surface-modified silicates, surface-modified glass fibers, surface-modified boron nitride.

The structures of the small molecule hydrocarbon group, the polymer chain residue, the small molecule silane chain residue, the inorganic small molecule chain residue and the inorganic large molecule chain residue are not particularly limited, and may be straight chain type, branched chain type, star type, comb type, dendritic type, monocyclic type, polycyclic type, spiro type, fused ring type, bridged ring type, chain type with a ring structure, two-dimensional and three-dimensional cluster type and combinations thereof; the polymer may contain flexible chain segment, rigid chain segment, or both flexible and rigid chain segments in small molecule alkyl, polymer chain residue, small molecule silane chain residue, inorganic small molecule chain residue, and inorganic large molecule chain residue.

The "single bond" as used herein refers to a common covalent bond formed by sharing a pair of electrons between two atoms in a compound molecule, and may be selected from a boron-boron single bond, a carbon-carbon single bond, a carbon-nitrogen single bond, a nitrogen-nitrogen single bond, a boron-carbon single bond, a boron-nitrogen single bond, a boron-silicon single bond, a silicon-carbon single bond, and a silicon-nitrogen single bond.

The "heteroatom linking group" as used herein may be any suitable heteroatom-containing linking group which may be selected from any one or a combination of any of the following: an ether group, a sulfur group, a disulfide group, a sulfide group, a divalent tertiary amine group, a trivalent tertiary amine group, a divalent silicon group, a trivalent silicon group, a tetravalent silicon group, a divalent phosphorus group, a trivalent phosphorus group, a divalent boron group, and a trivalent boron group.

The "organic group" as used herein means 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 polymer chain residue having a molecular weight of more than 1000Da, and suitable groups include, for example: methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde, acetyl, acetonyl, and the like.

The "organosilicon group" as used herein means a group mainly composed of a silicon element and a hydrogen element as a skeleton, and may be a small molecule silyl group having a molecular weight of not more than 1000Da or a silicone-based polymer chain residue having a molecular weight of more than 1000Da, and suitable groups are, for example: silane groups, siloxane groups, silasulfanyl groups, silazane groups, and the like.

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

In the present invention, a compound in which a carbon atom at any position of a hydrocarbon is substituted with a heteroatom is collectively referred to as "heterohydrocarbon".

The term "alkyl" as used herein refers to a saturated hydrocarbon group having a straight or branched chain structure. Where appropriate, alkyl groups may have the meaningWith a given number of carbon atoms, e.g. C_1-4An alkyl group including alkyl groups having 1,2,3, or 4 carbon atoms in a linear or branched arrangement. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-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 in the present invention refers to a saturated cyclic hydrocarbon. The cycloalkyl ring 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 "aryl" as used herein means any stable monocyclic or polycyclic carbocyclic ring 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, bianthryl, phenanthryl, biphenanthryl.

The term "heteroaromatic hydrocarbyl" as used herein denotes a stable monocyclic or polycyclic ring of up to 7 atoms in each ring, wherein at least one ring is aromatic and at least one ring contains heteroatoms selected from O, N, S, P, Si, B, and the like. Heteroarylalkyl groups within the scope of this definition include, but are not limited to, acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, quinazolinyl, pyrazolyl, indolyl, benzotriazolyl, furanyl, thienyl, thiophenyl, 3, 4-propylenedioxythiophenyl, benzothiophenyl, benzofuranyl, benzodioxan, benzodioxine, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, tetrahydroquinoline, 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.

The monocyclic structure mentioned in the cyclic structure of the present invention means that the cyclic structure contains only one ring, and examples thereof are:

the polycyclic structure referred to means that the cyclic structure contains two or more independent rings, such as:

the spiro ring structure refers to a cyclic structure containing two or more rings which are formed by sharing an atom with each other in the cyclic structure, for example:

reference to fused ring structures (which also includes bicyclic, aromatic and fused ring structures) is intended to include within the ring structure a ring structure made up of two or more rings sharing two adjacent atoms with one another, such as, for example:

the bridged ring structure mentioned above means a ring structure containing two or more rings which are constituted by sharing two or more adjacent atoms with each other in a ring structure, and has a three-dimensional cage structure, for example:

reference to nested ring structures refers to ring structures comprising two or more rings connected to or nested within one another, such as, for example:

for simplicity, the range of carbon atoms in a group is also indicated herein by the subscript of C in the subscript form indicating the number of carbon atoms the group has, e.g., C_1-10Denotes "having 1 to 10 carbon atoms", C_3-20Means "having 3 to 20 carbon atoms". "unsaturated C_3-20Hydrocarbyl "means C_3-20A compound having an unsaturated bond in a hydrocarbon group. "substituted C_3-20Hydrocarbyl "means C_3-20A compound obtained by substituting a hydrogen atom of a hydrocarbon group. "hybrid C_3-20Hydrocarbyl "means C_3-20A compound obtained by substituting a carbon atom in the hydrocarbon group with a hetero atom. When one group can be selected from C_1-10When hydrocarbyl, it may be selected from hydrocarbyl groups of any number of carbon atoms in the range indicated by the subscript, i.e., may be selected from C₁、C₂、C₃、C₄、C₅、C₆、C₇、C₈、C₉、C₁₀Any of hydrocarbon groups. In the present invention, unless otherwise specified, subscripts set forth as intervals each represent an integer selected from any one of the ranges, including both endpoints.

When the structure concerned has an isomer, any of the isomers may be used unless otherwise specified. If not specifically stated, alkyl means a hydrocarbon group formed by losing a hydrogen atom at any position. Specifically, for example, propyl means any of n-propyl and isopropyl, and propylene means any of 1, 3-propylene, 1, 2-propylene and isopropylene.

The term "substituted" as used herein means that any one or more hydrogen atoms at any position of the "substituted hydrocarbon group" may be substituted with any substituent, for example, a "substituted hydrocarbon group". The substituent is not particularly limited, and the like.

For a compound, a group or an atom, both substituted and hybridized, e.g. nitrophenyl for a hydrogen atom, also e.g. -CH₂-CH₂-CH₂-is replaced by-CH₂-S-CH(CH₃)-。

For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or. For example, the "and/or" in the specification of the organoboron compound (I) containing an organoboronic acid group and/or an organoboronate group "means that the organoboron compound (I) may contain only the organoboronic acid group, only the organoboronate group, or both the organoboronic acid group and the organoboronate group; for another example, in the specification, "A" is a module containing an organoboronic acid group and/or an organoborate group "and/or" means that A is a module containing an organoboronic acid group, or a module containing an organoborate group, or a module containing both an organoboronic acid group and an organoborate group. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.

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

In the invention, for the organic boric acid group and the organic boric acid ester group which form the dynamic polymer organic boric acid silicon ester bond, the boron atom in the group has electron deficiency, so that the group is easy to be attacked by nucleophilic reagent containing unshared electron pair to generate bonding; for the silicon hydroxyl group (including the silicon hydroxyl precursor capable of obtaining the silicon hydroxyl group through conversion) forming the organic borate silicon ester bond, as the silicon hydroxyl oxygen atom contains unshared electron pairs and the silicon hydroxyl group has strong polarity and high activity, the reaction such as a rapid dehydration condensation reaction, an ester exchange reaction and the like can be carried out to form the organic borate silicon ester bond in the process of contacting with the organic borate group and/or the organic borate group, so that dynamic covalent crosslinking and the like are formed. The invention utilizes the high reactivity of organic boric acid group and organic borate group with silicon hydroxyl and the strong dynamic reversibility of organic borate silicon ester bond to prepare the dynamic polymer which can show dynamic effect under mild condition. Meanwhile, the organic boric acid group and/or the organic borate group are used for forming the organic borate silicone bond, so that the components for forming the organic borate silicone bond are more abundant in selection, the regulation and control performance in the aspects of the structure, the dynamic reversibility, the mechanical property, the solvent resistance and the like of the dynamic polymer is greatly improved, and the application range of the polymer is expanded.

When the organoboron compound (I) containing the organoboronic acid group and/or the organoboronate group is mixed with the silicon-containing compound (II) containing the silicon hydroxyl group and/or the silicon hydroxyl precursor in a dissolved or molten state, the organoboronic acid group in the organoboron compound (I) can perform a rapid condensation reaction with the silicon hydroxyl group in the silicon-containing compound (II) to form an organoboronate-silicon ester bond, so as to obtain a dynamic monomer and/or prepolymer and/or polymer; the organoborate group in the organoboron compound (I) can directly perform ester exchange reaction with the silicon hydroxyl in the silicon-containing compound (II) to form an organoborate silicon ester bond, or can form an organoborate silicon ester bond by performing condensation reaction with the silicon hydroxyl in the silicon-containing compound (II) after forming an organoborate group by hydrolysis, so as to obtain a dynamic monomer and/or a prepolymer and/or a polymer; the silicon hydroxyl precursor in the silicon-containing compound (II) can be directly subjected to condensation reaction with the organic boric acid group in the organic boron compound (I) through small molecule removal, or can be subjected to condensation reaction with the organic boric acid group in the organic boron compound (I) after the silicon hydroxyl group is formed through hydrolysis, or is subjected to ester exchange reaction with the organic boric acid group in the organic boron compound (I) to form an organic boric acid silicone ester bond, so that the dynamic monomer and/or the prepolymer and/or the polymer are obtained. When the reaction is carried out using the organoboron compound (I) containing organoborate groups or the silicon-containing compound (II) containing silicon hydroxyl group precursors, it is generally necessary to carry out the reaction at a relatively high temperature, or to carry out the condensation reaction after in situ hydrolysis of one of them. One polymerization system may contain both of the organoboron compound (I) and the silicon-containing compound (II).

In general, for the compound (III) containing both an organoboronic acid group and/or organoboronate group and a silicon hydroxyl group and/or a silicon hydroxyl group precursor, it is necessary to react the organoboronic acid group in the compound (III) with a silicon hydroxyl group precursor contained in the same or different compound (III) to form an organoboronate silicone ester bond, or react the organoboronate group in the compound (III) with a silicon hydroxyl group precursor contained in the same or different compound (III) to form an organoboronate silicone ester bond, or hydrolyze the organoboronate group in the compound (III) to obtain an organoboronic acid group and then react with a silicon hydroxyl group precursor contained in the same or different compound (III) to form an organoboronate silicone ester bond, or react the organoboronate group in the compound (III) with a silicon hydroxyl group precursor contained in the same or different compound (III) to form an organoboronate silicone ester bond, or control the reaction conditions and the addition of a suitable reaction assistant The precursor is firstly hydrolyzed to obtain silicon hydroxyl, and condensation reaction is carried out to form organic boric acid silicon ester bond, or the organic boric acid ester group in the compound (III) and the silicon hydroxyl precursor are simultaneously hydrolyzed and then condensation reaction is carried out to form the organic boric acid silicon ester bond, so as to obtain the dynamic polymer. A polymerization system may contain, in addition to one or more compounds (III), one or more organoboron compounds (I) and/or one or more silicon-containing compounds (II).

In the embodiment of the present invention, in addition to the reaction of the organoboron acid group and/or organoborate group contained in the compound with the silicon hydroxyl group and/or silicon hydroxyl precursor in the process of forming the dynamic monomer and/or prepolymer and/or polymer, the organoboron compound (I), the silicon-containing compound (II), and the compound (III) can also be commonly covalently linked by polymerization reaction with other components, such as the compound (IV) and/or the compound (V), by using other reactive groups contained in the organoboron compound (I), the silicon-containing compound (II), and the organoborate group and the silicon hydroxyl precursor, to jointly react to form the hybrid cross-linked network of the dynamic polymer. The organoboron compound (I), silicon-containing compound (II), prepolymer and/or polymer in which the compound (III) participates can also be blended with other components such as compound (IV) and/or compound (V), and then a dynamic polymer of a hybrid cross-linked network is formed by ordinary covalent bonding of the other components. Or the ordinary covalent connection can be formed first, and then the dynamic covalent organic boric acid silicon ester bond is formed.

As the compound (IV), it is generally obtained by mutual reaction between other reactive groups contained in the compound (IV) or by mutual reaction between other reactive groups contained in the compound (IV) and the compound (V) and/or the prepolymer formed by participation of the organoboron compound (I), the silicon-containing compound (II), the compound (III) and/or other reactive groups contained in the polymer, to thereby obtain the hybrid crosslinked dynamic polymer containing organoboronate silicone bonds. It is also possible to form the usual covalent linkage directly from other reactive groups which the compound (IV) itself contains. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.

In embodiments of the invention, the other reactive groups may be reacted to give a common covalent bond, for example by reaction of the following form, to form a dynamic polymer together with the organoboronate silicone bond: forming an amide bond by a condensation reaction of an amino group contained in the compound and a carboxyl group contained in the compound; the epoxy group contained in the compound and the amino group and the sulfhydryl group contained in the compound are subjected to ring-opening reaction to form a secondary amine bond and a thioether bond; under the action of an initiator or external energy, carrying out free radical polymerization through olefin groups contained in the compound; 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 thiourethane 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; carrying out CuAAC reaction through an azide group contained in the compound and an alkynyl group contained in the compound under the catalysis of cuprous; carrying out thiol-ene click reaction through sulfydryl contained in the compound and alkylene contained in the compound; by addition reaction between double bonds contained in the compound, etc.; among them, preferred are ways to react rapidly at not more than 100 ℃, more preferred ways to react rapidly at room temperature, including but not limited to the reaction of isocyanate groups with amino groups, hydroxyl groups, thiol groups, acrylate reactions, thiol-ene click reactions.

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

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

In particular embodiments, the starting compound materials may be prepared by any suitable polymerization process commonly used in the art using any of the polymerization methods described above. For example, when the compound raw 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, etc.; for another example, when the compound raw 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, etc.; for another example, when the compound raw material is in the form of ionic polymerization to obtain a dynamic polymer, it may be carried out by a polymerization process such as solution polymerization, slurry polymerization, gas phase polymerization, or the like.

The melt polymerization mentioned in the above polymerization process is usually carried out by polymerizing compound raw materials in a molten state by using an initiator or conditions of light, heat, radiation, catalysis, etc. to obtain a dynamic polymer in a molten state; as mentioned, the solution polymerization is usually carried out by dissolving the compound raw materials and the initiator in an appropriate solvent to carry out polymerization to obtain a dynamic polymer; the interfacial polymerization mentioned above is usually carried out by dissolving the compound raw materials in two solvents which are not soluble with each other and carrying out polymerization at the interface of the solution (or on the side of the interfacial organic phase) to obtain a dynamic polymer; as mentioned, bulk polymerization is usually carried out by polymerizing compound raw materials under a small amount of initiator or conditions of light, heat, radiation, catalysis, etc. to obtain a dynamic polymer; as mentioned, the suspension polymerization is usually carried out by stirring a compound raw material in which an initiator is dissolved into small droplets, suspending the droplets in an aqueous medium, and polymerizing to obtain a dynamic polymer; the emulsion polymerization mentioned above is usually carried out by dispersing the compound raw materials in an aqueous medium in which an initiator is dissolved by the action of an emulsifier to form an emulsion and then carrying out polymerization to obtain a dynamic polymer; the slurry polymerization mentioned above is usually carried out by dissolving the compound raw material in a suitable solvent, and the initiator is present in the solvent in the form of dispersion to carry out the polymerization, and the obtained dynamic polymer is precipitated in the form of precipitate; as mentioned, the gas phase polymerization is usually carried out by polymerizing the compound raw materials in a gas phase by using an initiator or conditions of light, heat, irradiation, catalysis, etc. to obtain a dynamic polymer.

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 reducing system viscosity, being easy for mass and heat transfer, being convenient for temperature control and avoiding local overheating, and the obtained solution and emulsion are convenient for concentration or dispersion and are beneficial to coating, mixing and other operations.

The organoboron compound (I), silicon-containing compound (II), compound (III), compound (IV), compound (V) used for preparing the dynamic polymer may be in the form of gas, liquid, crystal, powder, granule, gel, paste, etc.

In the preparation of the dynamic polymer, the organoboronic acid in the organoboron compound (I), compound (III) as a raw material may be present in the form of an organoboronic acid or an organoboronate. The silicon hydroxyl group in the silicon-containing compound (II) or the compound (III) as a raw material may be present in the form of a silicon hydroxyl group or a silicon hydroxyl group precursor.

During the synthesis and use of the silicon-containing compound (II) as a starting material, condensation inhibitors may optionally be added, generally in order to maintain the system at neutral or near neutral conditions, to avoid condensation of the silicon hydroxyl groups to siloxanes, and thus to enable high yields of silicon hydroxyl group-containing compounds to be obtained. In the using process of the silicon-containing compound (II), the synthesized or hydrolyzed silicon-containing compound (II) is ensured to be used as well as possible; it is more preferable that the silicon-containing compound (II) is synthesized or hydrolyzed and then subjected to condensation reaction with the organoboron compound (I) under controlled conditions to give a dynamic polymer. In the process of reacting the silicon-containing compound (II) with the organoboron compound (I), the organoboron compound (I) to be reacted therewith is added to the organoboron compound (I) in the form of slowly adding or dropping as far as possible in the state where the organoboron compound (I) to be reacted therewith is in an excess amount.

When the raw material is selected from the compound (III), in order to ensure the stability of the raw material, the organic boric acid in the compound (III) is preferentially selected to exist in the form of organic boric acid ester, the silicon hydroxyl in the compound (III) is preferentially selected to exist in the form of silicon hydroxyl precursor, and in the preparation process of the compound (III), a nonpolar inert solvent is used as a reaction solvent as much as possible, and the compound (III) is stored under the condition of low temperature; meanwhile, some condensation inhibitors are also needed to be added in the synthesis process of raw materials, and the compound (III) is ensured to be used at present. Considering that the mode and method adopted by the compound (III) in the preparation and preservation processes are relatively complicated, the raw material components for preparing the dynamic polymer are preferably selected from the organoboron compound (I) and the silicon-containing compound (II), but the compound (III) is also one of the important components of the dynamic polymer raw material, has specific advantages in certain specific cases and cannot be ignored.

When reactant raw materials are mixed in a dissolved or molten state, the organic boric acid group and/or the organic boric acid ester group in the reactant and the silicon hydroxyl and/or the silicon hydroxyl precursor can be subjected to dynamic covalent crosslinking under the conditions of heating, radiation, illumination and the like, or can be subjected to dynamic covalent crosslinking under the action of additives such as an initiator, a catalyst and the like to generate an organic boric acid silicon ester bond.

In the preparation process of the dynamic polymer, for the dynamic polymer with a first network structure (containing only one cross-linking network, and the cross-linking network contains organic borate silicon ester bond cross-linking and supermolecule hydrogen bond cross-linking), the dynamic polymer can be obtained by utilizing at least one organic boron compound (I) and at least one silicon-containing compound (II) to participate in the reaction to generate organic borate silicon ester bond and supermolecule hydrogen bond for hybrid cross-linking; or at least one compound (III) which participates in the reaction with at least one organic boron compound (I) and/or at least one silicon-containing compound (II) to generate organic boric acid silicon ester bonds and supermolecular hydrogen bonds for hybrid crosslinking; or at least one compound (IV) or at least one compound (V) which participates in the reaction to generate a common covalent bond to carry out hybrid crosslinking; wherein at least one organoboron compound (I) or at least one silicon containing compound (II) or at least one compound (III) contains one or more further reactive groups.

For a dynamic polymer having a second network structure comprising two crosslinked networks, one containing only organoboronate silane linkages and the other containing only supramolecular hydrogen linkages, the network structure comprising only crosslinked networks crosslinked with organoboronate silane linkages, obtainable by dynamic covalent crosslinking using at least one organoboron compound (I) and at least one silicon-containing compound (II) which react to form organoboronate silane linkages, or at least one compound (III), or which is reacted with at least one organoboron compound (I) and/or at least one silicon-containing compound (II) to form organoboronate silane linkages; the network structure only contains a cross-linked network of supramolecular hydrogen bond cross-linking, and the network structure can be obtained by utilizing at least one compound (V) to participate in reaction to generate supramolecular hydrogen bond for cross-linking, or prepared by utilizing at least one existing polymer containing supramolecular hydrogen bond cross-linking as a raw material.

Similarly, for dynamic polymers with other hybrid cross-linked network structures, the network structure only contains a cross-linked network of organic borate silicon ester bond cross-linking, only contains a cross-linked network of supramolecular hydrogen bond cross-linking, and simultaneously contains a cross-linked network of organic borate silicon ester bond cross-linking and supramolecular hydrogen bond cross-linking, and the dynamic polymers can be respectively prepared by using corresponding compound raw materials according to the thought.

In the preparation process of the dynamic polymer, after the compounds as raw materials participate in reaction, the raw material components can be polymerized/crosslinked by taking organic boric acid silicon ester bonds and hydrogen bonds as linking points, so that the dynamic polymer with higher molecular weight is obtained. It is not required that all functional groups and other reactive groups in the starting components completely react with each other to form ordinary covalent bonds and dynamic covalent bonds, provided that the ordinary covalent bonds and dynamic covalent bonds formed are sufficient to maintain the hybrid cross-linked network structure of the dynamic polymer.

For the dynamic polymer containing two or more crosslinked networks, the dynamic polymer having the second network structure and the dynamic polymer having the third network structure as described in the present invention can be prepared by a stepwise method or a simultaneous method.

For example, for a dynamic polymer having a double-network structure, when the dynamic polymer is prepared by a step-by-step method, a first network may be prepared by using a monomer or a prepolymer, a catalyst, and an initiator, and then a second network prepared may be added and blended to obtain a cross-linked network blended with each other, wherein the second network may be swollen by a solvent and then blended with the first network; or preparing a first network, placing the crosslinked first network into a second network monomer or prepolymer melt or solution containing a catalyst, an initiator and the like to swell the first network, and then polymerizing and crosslinking the second network monomer or prepolymer in situ to form a second network to obtain a (partially) interpenetrating crosslinked network, wherein the crosslinking degree of the first network is preferably slight crosslinking above a gel point so as to facilitate the interpenetrating effect of the second network; by analogy, for a dynamic polymer containing a multi-network structure, a plurality of mutually blended or mutually interpenetrated cross-linked networks can be obtained by adopting a similar fractional step method.

For example, for a dynamic polymer containing a double-network structure, when the dynamic polymer is prepared by a synchronous method, two prepared cross-linked networks can be placed in the same reactor to be blended to obtain a cross-linked network which is blended with each other, wherein the cross-linked networks can be swelled by means of a solvent and then blended; it is also possible to mix two or more monomers or prepolymers and react them in the same reactor according to the respective polymerization and crosslinking sequences to give (partially) interpenetrating crosslinked networks.

In the process of preparing the dynamic polymer with the hybrid crosslinking network by using the organic boron compound (I), the silicide (II), the compound (III), the compound (IV) and the compound (V), organic structures such as functional groups, molecular chain segments with different structures, molecular chain segments with different molecular weights, reactive groups, functional groups and the like can be introduced into compound raw materials according to requirements through the design and adjustment of the structure of the compound, and the organic structures become structural components of the dynamic polymer through the preparation process, so that the regulation and control of the structure of the dynamic polymer are realized in a large range. The diversity of the dynamic polymer structure also enables the polymer to show various performances, and the polymer can be applied to different fields according to the performances of the polymer. More importantly, the structure and the performance of the polymer can be designed from the source according to the requirements of practical application by those skilled in the art; in this process, the organic structures (e.g., organoboron structures, organosilicon structures) used can become effective media for the skilled person to regulate and design dynamic polymer structures.

Wherein, by designing the functional group structures in the organic boron compound (I), the silicon-containing compound (II) and the compound (III), the dynamic polymers with different dynamic activities can be prepared. For example, a dynamic polymer is prepared by using a phenylboronic acid/phenylboronic acid ester structure with an aminomethyl group attached to the ortho position or a phenylboronic acid/phenylboronic acid ester structure with an amide group attached to the ortho position, wherein the aminomethyl group or the amide group at the ortho position can play a role in promoting the dynamic property; for example, after a strong electron-withdrawing group (such as a fluorine atom, an acetoxy group, a pyridyl group, a piperidyl group and the like) is connected to a boron atom in the organoboronic acid group and/or the organoboronic acid group, the reaction rate of the organoboronic acid group and/or the organoboronic acid group with a silicon hydroxyl group and/or a silicon hydroxyl group precursor is also greatly improved; the obtained dynamic polymer can show higher dynamic activity, so that the organic boric acid silicon ester bond in the polymer can show dynamic reversibility under a milder condition, and the dynamic polymer can be prepared and used under a milder condition, thereby expanding the application range of the polymer.

In the preparation process of the dynamic polymer, the number of functional groups and the number of hydrogen bond groups in the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) are regulated, so that the dynamic polymer with different crosslinking degrees can be prepared, and the performance of the dynamic polymer is different along with the difference of the crosslinking degrees. For materials made with dynamic polymers that are less crosslinked, they typically have lower mechanical strength and modulus, superior toughness and ductility, and poor thermal and dimensional stability, and are generally soft in texture, have low surface hardness, and can be stretched over a large range in macroscopic manifestations. For materials made from dynamic polymers with higher cross-linking, the mechanical strength and modulus are generally higher, and the toughness, thermal stability, wear resistance and creep resistance are all improved, but the ductility is reduced, and the materials are generally colloid or solid with better rebound resilience or rigidity in macroscopic representation.

In the present invention, at least one dynamic covalent cross-linking and at least one supramolecular hydrogen bond cross-linking are used to prepare a dynamic polymer with a hybrid cross-linked network. For the traditional cross-linked polymer, the cross-linked polymer is generally prepared by common covalent cross-linking, the obtained cross-linked polymer is lack of dynamic property, once the common covalent bond is broken, the polymer is permanently damaged, and has no responsiveness under the external stimulation effect, so that the functional characteristics of self-repairing, recoverability, reworkability and the like cannot be embodied, and the performance and the application field of the cross-linked polymer are greatly limited; in addition, the traditional cross-linked structure has no intermolecular slip effect and generally higher bond breaking energy, and basically needs to provide toughness by depending on the elongation of the segment between cross-linking points under stress, so that the obtained cross-linked polymer generally has poorer toughness. The conventional supramolecular hydrogen bond crosslinked polymer has poor general stability and mechanical property, often cannot meet the requirement of practical use, and has a plurality of limitations on application and popularization. The organic boric acid silicon ester bond and the supermolecule hydrogen bond contained in the dynamic polymer with the hybrid cross-linking network prepared by utilizing the dynamic covalent bond and the supermolecule hydrogen bond can be broken in a mode of a 'sacrificial bond' under the action of external force, so that on one hand, a large amount of energy can be dissipated, and excellent tensile toughness and tear resistance are provided for the cross-linking polymer in a specific structure; on the other hand, super stretching elongation can be obtained; in addition, self-repairability, moldability, reworkability can be obtained. Meanwhile, the dynamic property of the dynamic polymer is further improved through the dual regulation and control functions of the dynamic covalent bond and the supermolecule hydrogen bond, the energy dissipation mode is more diversified, and the supermolecule hydrogen bond and the organic boric acid silicon ester bond can be changed in sequence when being damaged by external force, so that the force is dissipated step by step, and the resistance of the material to the external force is improved. In addition, as the organic boron silicate ester bond in at least one crosslinking network reaches above the gel point, when the material is impacted by fast external impact, the organic boron silicate ester bond crosslinking can endow the dynamic polymer with fast viscosity-elasticity transformation, thereby being convenient to obtain a balanced structure of the material under the impact state and disperse impact force, and lightening impact injury.

In the preparation process of the dynamic polymer, the molecular chain flexibility of the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) is regulated, so that the dynamic polymer with different properties can be prepared, and the obtained dynamic polymer can have one or more glass transition temperatures. For compounds consisting essentially of flexible chains (e.g., polyethylene chains, polysiloxane chains, polybutadiene chains, polyacrylic chains, polyester chains, etc.) and/or compounds that can be polymerized into flexible chains, the dynamic polymers made therefrom are relatively easy to rotate within the molecular chain, typically having a low glass transition temperature (typically no higher than 25 ℃) and a low melting point (typically no higher than 100 ℃). For compounds mainly composed of rigid chains (such as polyacetylene chains, polyaramid chains, polyphenylene ether chains, polybenzothiazole chains, and the like) and/or compounds capable of polymerizing into rigid chains, dynamic polymers prepared therefrom have relatively difficulty in rotation within molecular segments, generally have high glass transition temperatures (generally higher than 25 ℃) and high melting points (generally higher than 100 ℃), and have high melt viscosities; materials generally exhibit macroscopically superior mechanical properties, better dimensional stability, heat resistance, and chemical resistance, but lower ductility. When a compound containing a flexible chain and a rigid chain and/or a compound capable of being polymerized into the flexible chain and the rigid chain are/is adopted at the same time, the prepared dynamic polymer generally has a plurality of glass transition temperatures with obvious differences, the polymer material has moderate rigidity, hardness and flexibility, and the mechanical property of the polymer material can be adjusted according to different formulas. In the present invention, since the dynamic polymer having a flexible structure can exhibit more excellent dynamic reversibility and tensile toughness, it is preferable to prepare the dynamic polymer using the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV), and the compound (V) having a flexible structure and/or capable of polymerizing into a flexible chain.

In the preparation process of the dynamic polymer, the molecular weights of the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) are regulated, so that the dynamic polymer with different crosslinking densities can be prepared, and the dynamic polymer also shows different property characteristics due to different crosslinking densities. The lower the crosslink density of the dynamic polymer, the higher the molecular weight of the polymer chains between crosslinking points and vice versa. For dynamic polymers with low crosslinking density, the glass transition temperature and the melting point are generally low, the rigidity and the surface hardness are low, the mechanical strength is low, but the dynamic polymer can show good dynamic activity; for dynamic polymers with higher crosslinking density, the glass transition temperature and the melting point are generally higher, and the dynamic polymers can show better mechanical strength, toughness and elasticity, but the dynamic activity is reduced. The person skilled in the art can adjust the process according to the actual needs.

In addition, in the preparation process of the dynamic polymer, the performance of the dynamic polymer can be regulated and controlled by introducing functional groups into the organic boron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V). For example, hydrolysis resistance of dynamic polymers is improved by introducing hydrophobic groups; preparing a dynamic polymer with fluorescence by introducing a fluorescent group; the oxidation resistance of the dynamic polymer is improved by introducing an antioxidant group; the dynamic properties of the dynamic polymer are adjusted by introducing acidic groups or basic groups, and the like. For another example, when it is desired to blend the dynamic polymer with other polymers, the compatibility between the components can be improved by introducing structural components or coupling groups similar to those of other polymers.

For example, the above description is only an example of the part of the structure of the compound component as the raw material in the present invention that can regulate the performance of the dynamic polymer, and the design of the structure, performance and use of the dynamic polymer in the present invention has a wide adjustable range, often can also embody many unexpected practical effects, and is difficult to exhaust, and those skilled in the art can adjust the structure, performance and use according to the idea of the present invention.

In the embodiment of the present invention, the acrylic group and the acrylate group contained in the dynamic polymer of polyacrylate type are preferably obtained by introducing an acrylic monomer to react in the form of radical polymerization or radical copolymerization. Wherein, the acrylic monomer includes but is not limited to: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, t-butyl acrylate, 2-ethyl acrylate, n-octyl acrylate, decyl acrylate, 2-ethoxyethyl acrylate, 2-cyanoethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, lauryl acrylate, trifluoroethyl methacrylate, glycidyl methacrylate, and the like.

In the preparation process of the invention, the group L, the group J, the group T and the group Y are polyacrylic acid chain residue, polymethyl acrylate chain residue, polymethyl methacrylate chain residue or other organic boron compounds (I), silicon-containing compounds (II), compounds (III), compounds (IV) and compounds (V) containing acrylic groups and acrylate group structures, which are respectively selected as raw materials, and the polymerization/crosslinking reaction among the raw materials of the compounds is utilized to prepare the polyacrylate dynamic polymer.

In the embodiment of the present invention, the olefin polymer segment contained in the dynamic polymer of polyolefin type is preferably obtained by introducing an olefin monomer to react in the form of radical polymerization or radical copolymerization. Wherein, the vinyl monomers include, but are not limited to: ethylene, propylene, butene, isobutylene, butadiene, isoprene, chloroprene, styrene, vinyl chloride, vinylidene chloride, vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, alkyl vinyl ether, vinyl acetate, norbornene, and the like.

In the preparation process of the invention, the group L, the group J, the group T and the group Y are respectively selected from 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, polychlorotrifluoroethylene chain residues, polyvinyl acetate chain residues, polyvinyl alkyl ether chain residues, polybutadiene chain residues, polyisoprene chain residues, polychloroprene chain residues, polynorbornene chain residues or other organic boron compounds (I), silicon-containing compounds (II), silicon-containing compounds (III), compounds (IV) and compounds (V) containing olefin polymer chain segment structures as raw materials, and the polyolefin dynamic polymer is prepared by utilizing polymerization/crosslinking reaction among the raw materials of the compounds.

In the embodiment of the present invention, the urethane, urea, and thiocarbamate groups contained in the polyurethane-based dynamic polymer are preferably obtained by reacting an isocyanate group with a group having an active hydrogen such as a hydroxyl group, an amino group, or a mercapto group.

In the preparation process of the invention, the group L, the group J, the group T and the group Y are respectively selected as a polyurethane chain residue, a polyurea chain residue, a polythiourethane chain residue or other organic boron compounds (I), silicon-containing compounds (II), compounds (III), compounds (IV) and compounds (V) containing urethane, urea and thiocarbamate structures to be used as raw materials, and the polymerization/crosslinking reaction among the raw materials of the compounds is utilized to prepare the dynamic polymer of polyurethane. The polyurethane dynamic polymer can also be prepared by introducing a certain amount of isocyanate groups and certain amounts of hydroxyl groups, amino groups and mercapto groups into the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) and then using the isocyanate groups and the hydroxyl groups, the amino groups and the mercapto groups as one of other reactive groups, and by the addition reaction between the isocyanate groups and the hydroxyl groups, the amino groups and the mercapto groups together with the organoboron silicate bonds; under the circumstances, the polyurethane dynamic polymer is generally prepared by a step method, namely, the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the isocyanate group contained in the compound (V) are fully reacted with the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the hydroxyl group, the amino group and the mercapto group contained in the compound (V) to generate a carbamate group, a carbamide group and a thiocarbamate group, and then the condensation reaction of the organoborate silicone bond is carried out under the controlled conditions, wherein, in order to ensure that the hydroxyl group, the amino group and the mercapto group contained in the compound raw materials are fully reacted with the isocyanate group, the number of the hydroxyl group, the amino group and the mercapto group contained in each compound raw material is preferably 1 to 4, and the molar number of the isocyanate group participating in the reaction in the system is more than that of the hydroxyl group, And the mole number of the amino and the mercapto is that after the hydroxyl, the amino and the mercapto in the system are completely reacted, condensation reaction of the organic boric acid group and/or the organic boric acid ester group and the silicon hydroxyl and/or the silicon hydroxyl precursor is carried out, so that the reaction for generating the organic boric acid silicon ester bond is independent of common covalent reaction of other reactive groups.

Because the dynamic polymers of polyacrylate, polyolefin and polyurethane have simple and mature preparation process, wide adjustable molecular structure, excellent and various performance parameters, good practical application capability and wide application field, the dynamic polymers can be rapidly put into production and application by utilizing a plurality of raw materials and ready-made process equipment which are used for preparing the polymers. Therefore, it is considered as a preferred embodiment of the dynamic polymer in the present invention. Similarly, by adjusting parameters such as the molecular structure, molecular weight, functionality, hydroxyl value, etc. of the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV), and the compound (V), parameters such as the hardness, flexibility, viscosity, foaming condition, etc. of the dynamic polymers of polyacrylates, polyolefins, and polyurethanes can also be controlled, and those skilled in the art can adjust the parameters according to actual situations.

In the embodiment of the present invention, the dynamic polymer form of the hybrid crosslinked network can be solution, emulsion, paste, common solid, gel (including hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel, ionic liquid swollen gel), foam, etc., wherein the content of soluble small molecular weight components in the common solid and the foam is generally not higher than 10 wt%, and the content of small molecular weight components in the gel is generally not lower than 50 wt%.

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

In the preparation process of the dynamic polymer, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted to foam the dynamic polymer.

The mechanical foaming method is that during the preparation of dynamic polymer, large amount of air or other gas is introduced into emulsion, suspension or solution of polymer via strong stirring to form homogeneous foam, which is then gelled and solidified via physical or chemical change to form foamed material. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.

The physical foaming method is to realize 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, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into polymer particles under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt and starch with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into plastic and then are solidified to form closed-cell foamed plastic; among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer. The physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like. In addition, the preparation method can also adopt a freeze drying method.

The chemical foaming method is a method for foaming a dynamic polymer by generating gas accompanied by a chemical reaction in a foaming process of the dynamic polymer, and generally includes the following two methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) to cause the polymer to expand and foam. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

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

The mould pressing foaming molding has a simple process and is easy to control, and can be divided into a one-step method and a two-step method. The one-step molding means that the mixed materials are directly put into a mold cavity for foaming molding; the two-step method is to pre-foam the mixed materials and then put the materials into a die cavity for foaming and forming. Wherein, the one-step method is more convenient to operate and has higher production efficiency than the two-step method, so the one-step method is preferred to carry out the mould pressing foaming molding.

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

The process and equipment of the extrusion foaming molding are similar to those of common extrusion molding, a foaming agent is added into an extruder before or in the extrusion process, the pressure of a melt flowing through a machine head is reduced, and the foaming agent is volatilized 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 has competitive cost compared with injection foam molding.

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

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

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

In embodiments of the present invention, dynamic polymer foams can be further classified by their density into low-foaming, medium-foaming, and high-foaming. Low-foaming foams having a density of more than 0.4g/cm³The foaming multiplying power is less than 1.5; the medium-foamed foam material has a density of 0.1-0.4 g/cm³The foaming ratio is 1.5-9; and a high-foaming foam material having a density of less than 0.1g/cm³The expansion ratio is greater than 9.

The raw material components for preparing the dynamic polymer comprise other polymers which can be added, addition agents which can be added and reaction products of the organic boron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) which form the dynamic polymer with the hybrid crosslinking network together in a blending mode.

The additive polymer can be used as an additive to improve the material performance, endow the material with new performance, improve the use and economic benefits of the material and achieve the comprehensive utilization of the material in a system. Other polymers may be added, which may be selected from natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers. The invention does not limit the character and molecular weight of the added polymer, and can be oligomer or high polymer according to the difference of molecular weight, and can be homopolymer or copolymer according to the difference of polymerization form, and the polymer is selected according to the performance of the target material and the requirement of the actual preparation process in the specific using process.

When the other polymer which can be added is selected from natural high molecular compounds, the polymer can be selected from any one or more of the following natural high molecular compounds: fur, natural rubber, cotton, hemp, asbestos, silk, raw lacquer, etc.

When the other polymer which may be added is selected from synthetic resins, it may be selected from any one or any of the following synthetic resins: polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinylidene chloride, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polymethyl acrylate, polymethyl methacrylate, polymethacrylonitrile, polyoxymethylene, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, polyethylene terephthalate, Ethylene-vinyl acetate copolymers, acrylonitrile-acrylate-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, polyvinylpyrrolidone, phenol resins, urea resins, unsaturated polyesters, and the like.

When the other polymer which may be added is selected from synthetic rubbers, it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, polysulfide rubber, urethane rubber, epichlorohydrin rubber, thermoplastic elastomer, and the like.

When the other polymer which may be added is selected from synthetic fibres, it may be selected from any one or any of the following synthetic fibres: viscose fibers, cuprammonium fibers, diethyl ester fibers, triethyl ester fibers, polyamide fibers, polyester fibers, polyurethane fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, polyolefin fibers, fluorine-containing fibers, and the like.

In the preparation process of the polymer material, other polymers which can be added are preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polymethyl methacrylate, phenolic resin, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, polyurethane rubber, thermoplastic elastomer.

The additive 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 selected from any one or any several of the following additives: the synthesis auxiliary agent comprises a catalyst and an initiator; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; the auxiliary agent for improving the mechanical property comprises a chain extender, a flexibilizer and a coupling agent; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer, a foaming agent and a dynamic regulator; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents include nucleating agents, rheological agents, thickening agents and leveling agents.

the catalyst in the additive which can be added is not limited to any one or more of catalysts for polyurethane synthesis such as amine catalysts like triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N '-trimethyl-N' -hydroxyethyldiaminoethyl ether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N' -tetramethylalkylenediamine, N, N, N ', N' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N, N-dimethylbenzylamine, N, N-dimethyldecadecylamine, N, N-dimethylhexadecylamine, N-dimethyloctylammonium chloride, potassium octylammonium chloride, potassium₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (A), (B), (C) and (C)TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate and the like, ④ thiol-ene reaction catalyst, photocatalyst such as benzoin dimethyl ether, 2-hydroxy-2-methylphenyl acetone, 2-dimethoxy-2-phenyl acetophenone and the like, nucleophile catalyst such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine and the like, and the amount of the catalyst used is not particularly limited, and is generally 0.01 to 0.5% by weight.

the initiator of the additive which can be added can cause the monomer molecules to activate to generate free radicals during the polymerization reaction, so as to improve the reaction rate and promote the reaction, and includes but is not limited to any one or more of initiators for radical polymerization such as organic peroxides, e.g., lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylperoxypivalate, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, azo compounds, e.g., Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides, e.g., ammonium persulfate, potassium persulfate, etc., initiators for living polymerization such as 2,2,6, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane, cuprous chloride, and bipyridine ternary system, ③ ionic polymerization such as butyllithium, sodium naphthalene system, boron trifluoride/water system, stannic chloride/haloalkane system, initiators for coordination, such as aluminum chloride, and potassium chloride, initiators for ring-opening polymerization such as triethylammonium chloride, potassium chloride, initiators for polymerization initiators such as 1.1.1.1.1.0.1 wt%, and initiators for polymerization initiators for methyl chloride, for ethylene bis (triethylammonium chloride), and stannous chloride).

the antioxidant in the additive can retard the oxidation process of polymer samples and ensure that the materials can be successfully processed and the service life of the materials can be prolonged, including but not limited to any one or more of hindered phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 ' -methylenebis (4-methyl-6-tert-butylphenol), sulfur-containing hindered phenols such as 4,4 ' -thiobis- [ 3-methyl-6-tert-butylphenol ], 2 ' -thiobis- [ 4-methyl-6-tert-butylphenol ], triazine hindered phenols such as 1,3, 5-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, trimeric isocyanates such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate, N- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) -hexahydro-triazine, trimeric isocyanates such as tris (3, 5-tert-butyl-4-hydroxybenzyl) -triisocyanate, N-bis [ β - (3, 5-butyl-4-hydroxyphenyl) phosphite ], tris (tert-butyl-4-hydroxyphenyl) phosphite, N-tert-butyl-4-butyl-tert-butyl-4-tert-butyl-phenyl) phosphite, N-butyl-4-tert-butyl-tert-hydroxyphenyl) phosphite, N-butyl-4-butyl-tert-butyl-4-tert-butyl-tert-butyl-phenyl) phosphite, N-tert-butyl-phenyl phosphite, BHT-butyl-phenyl phosphite, N-4-butyl-4-tert-butyl-phenyl phosphite, N-butyl-.

The light stabilizer in the additive can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and the additive comprises any one or more of the following light stabilizers: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; precursor type ultraviolet absorbers such as p-tert-butyl benzoate salicylate, bisphenol A disalicylate; ultraviolet ray quenchers, such as bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel; hindered amine light stabilizers such as bis (2,2,6, 6-tetramethylpiperidine) sebacate, 2,2,6, 6-tetramethylpiperidine benzoate, tris (1,2,2,6, 6-pentamethylpiperidyl) phosphite; other light stabilizers, such as 2, 4-di-tert-butyl-4-hydroxybenzoic acid (2, 4-di-tert-butylphenyl) ester, alkylphosphoric acid amide, zinc N, N '-di-N-butyldithiocarbamate, nickel N, N' -di-N-butyldithiocarbamate, etc.; among them, carbon black and bis (2,2,6, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.

The heat stabilizer in the additive can prevent the polymer sample from generating chemical changes due to heating in the processing or using process, or delay the changes to achieve the purpose of prolonging the service life, and the heat stabilizer comprises but is not limited to any one or more of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, isooctyl dimethyltin dimercaptoacetate; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di (n) -butyltin maleate are preferable as the heat stabilizer. The amount of the heat stabilizer to be used is not particularly limited, but is usually 0.1 to 0.5% by weight.

The chain extender in the additive can react with the reactive group on the molecular chain of the reactant to expand the molecular chain and increase the molecular weight, and the chain extender comprises but is not limited to any one or more of the following chain extenders: polyamine-type chain extenders, such as diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tetraethyldiphenylmethylenediamine, tetraisopropyldiphenylenediamine, m-phenylenediamine, tris (dimethylaminomethyl) phenol, diaminodiphenylmethane, 3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), 3, 5-dimethylthiotoluenediamine (DMTDA), 3, 5-diethyltoluenediamine (DETDDA), 1,3, 5-triethyl-2, 6-diaminobenzene (TEMPDA). The amount of the chain extender to be used is not particularly limited, and is generally 1 to 10% by weight.

The toughening agent in the additive can reduce the brittleness of a polymer sample, increase the toughness and improve the bearing strength of the material, and the toughening agent comprises any one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS) or chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited, but is generally 5 to 10% by weight.

The coupling agent in the additive can improve the interface performance of a polymer sample and an inorganic filler or a reinforcing material, reduce the viscosity of a material melt in the plastic processing process, improve the dispersion degree of the filler to improve the processing performance, and further enable a product to obtain good surface quality and mechanical, thermal and electrical properties, wherein the coupling agent comprises any one or more of the following coupling agents: organic acid chromium complex, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent and the like; among them, gamma-aminopropyltriethoxysilane (silane coupling agent KH550) and gamma- (2, 3-glycidoxy) propyltrimethoxysilane (silane coupling agent KH560) are preferable as the coupling agent. The amount of the coupling agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.

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

The release agent in the additive can make the polymer sample easy to release, smooth and clean, and includes but not limited to any one or more of the following release agents: paraffin, soaps, dimethyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicone rubber and the like; among them, the release agent is preferably dimethyl silicone oil. The amount of the release agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.

The plasticizer in the additive can increase the plasticity of a polymer sample, so that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation, flexibility and flexibility of the polymer are improved, and the plasticizer comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate and phthalic acidDioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, such as epoxyglycerides, epoxidized fatty acid monoesters, epoxidized tetrahydrophthalic acid esters, epoxidized soybean oil, epoxidized 2-ethylhexyl stearate, epoxidized 2-ethylhexyl soyate, 4, 5-epoxytetrahydrophthalic acid di (2-ethyl) hexyl ester, and methyl chrysene acetyl ricinoleate; glycol esters, e.g. C_5～9Acid ethylene glycol ester, C_5～9Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol-series ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester, phenyl petroleum sulfonate, trimellitate ester, citrate ester and the like; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited, but is generally 5 to 20% by weight.

The foaming agent in the additive can enable a polymer sample to be foamed into pores, so that a light, heat-insulating, sound-insulating and elastic polymer material is obtained, and the foaming agent comprises any one or more of the following foaming agents: 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, chlorotrifluoromethane; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylenetetramine, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azobisisobutyronitrile, 4 ' -oxybis-benzenesulfonylhydrazide, trihydrazinotriazine, p-toluenesulfonylaminourea, biphenyl-4, 4 ' -disulfonylazide; foaming promoters such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc. Among them, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylenetetramine (foaming agent H), and N, N ' -dimethyl-N, N ' -dinitrosoterephthalamide (foaming agent NTA) are preferable as the foaming agent, and the amount of the physical microsphere foaming agent and the amount of the foaming agent to be used are not particularly limited, but is usually 0.1 to 30 wt%.

The dynamic modifier in the additive can improve the dynamics of adjusting the organic boric acid silicon ester bond so as to obtain the optimized expected performance, and the dynamic modifier is generally a free compound with a free hydroxyl group or a free carboxyl group, including but not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid and the like. The amount of the dynamic adjusting agent to be used is not particularly limited, but is usually 0.1 to 10% by weight.

The antistatic agent in the additive can guide or eliminate harmful charges accumulated in a polymer sample, so that the polymer sample does not cause inconvenience or harm to production and life, and the antistatic agent comprises any one or more of the following antistatic agents: anionic antistatic agents such as alkylsulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate ester diethanolamine salts, potassium p-nonylphenyl ether sulfonates, phosphate ester derivatives, phosphates, phosphate ester derivatives, fatty amine sulfonates, sodium butyrate sulfonates; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium ethyl inner salt, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine ethyl inner salt, N-lauryl-N, N-dipolyoxyethylene-N-ethylphosphonic acid sodium salt, N-alkyl amino acid salts; nonionic antistatic agents such as fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene ether phosphate esters, glycerin fatty acid esters; high molecular antistatic agents such as polyallylamine N-quaternary ammonium salt substitutes, poly-4-vinyl-1-acetonylpyridinophosphoric acid-p-butylbenzene ester salts, and the like; among them, lauryl trimethyl ammonium chloride and alkyl phosphate diethanol amine salt (antistatic agent P) are preferable as the antistatic agent. The amount of the antistatic agent to be used is not particularly limited, but is generally 0.3 to 3% by weight.

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 is preferably used for emulsion polymerization, and the emulsifier comprises any one or more of the following emulsifiers: anionic type, such as higher fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, sodium alkylnaphthalenesulfonate, succinic acid ester sulfonate, petroleum sulfonic acid salts, castor oil sulfate ester salts, sulfated ricinoleic acid butyl ester salts, phosphate ester salts, fatty acyl-peptide condensates; cationic, such as alkyl ammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic types such as alkylphenol ethoxylates, polyoxyethylene fatty acid esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol and sorbitan fatty acid esters, sucrose fatty acid esters, alcohol amine fatty acid amides, and the like; the emulsifier is preferably sodium dodecyl benzene sulfonate, sorbitan fatty acid ester, and triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited, but is generally 1 to 5% by weight.

The dispersant in the additive can disperse solid floccules in the polymer mixed solution into fine particles to be suspended in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously prevent the particles from settling and coagulating to form a stable suspension, and the dispersant includes but is not limited to any one or more of the following dispersants: anionic type, such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium petroleum sulfonate; a cationic type; nonionic types, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicates, condensed phosphates, etc.; among them, sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (dispersant N) and fatty alcohol-polyoxyethylene ether are preferable as the dispersant. The amount of the dispersant used is not particularly limited, but is generally 0.3 to 0.8% by weight.

The colorant in the additive can make the polymer product present the required color and increase the surface color, and the colorant includes but is not limited to any one or several of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. lithol rubine BK, lake Red C, perylene Red, Jia-base R Red, Phthalocyanine Red, permanent magenta HF3C, Plastic scarlet R and Clomomor Red BR, permanent orange HL, fast yellow G, Ciba Plastic yellow R, permanent yellow 3G, permanent yellow H₂G. Phthalocyanine blue B, phthalocyanine green, plastic purple RL and aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil-soluble yellow, etc.; the colorant is selected according to the color requirement of the sample, and is not particularly limited. The amount of the colorant to be used is not particularly limited, but is generally 0.3 to 0.8% by weight.

The fluorescent whitening agent in the additive can enable the dyed material to obtain the fluorite-like flash luminescence effect, and the fluorescent whitening agent comprises any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like; among the fluorescent whitening agents, sodium diphenylethylene disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1) are preferable. The amount of the fluorescent whitening agent to be used is not particularly limited, but is generally 0.002 to 0.03% by weight.

The matting agent in the additive can diffuse reflection when incident light reaches the surface of the polymer to generate low-gloss matte and matte appearance, and the matting agent comprises any one or more of the following matting agents: settling barium sulfate, silicon dioxide, hydrous gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited, but is generally 2 to 5% by weight.

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

The nucleating agent in the additive can accelerate the crystallization rate, increase the crystallization density and promote the grain size to be micronized by changing the crystallization behavior of the polymer, so as to achieve the purposes of shortening the molding period of the material and improving the physical and mechanical properties of the product, such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like, 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, ethylene propylene rubber, ethylene propylene diene monomer and the like; wherein, the nucleating agent is preferably silicon dioxide and ethylene propylene diene monomer. The amount of the nucleating agent used is not particularly limited, but is generally 0.1 to 1% by weight.

The rheological agent in the additive can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevent the solid particles from settling during storage, and improve the redispersibility, and the rheological agent comprises any one or more of the following rheological agents: inorganic species 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, titanium chelates, aluminum chelates; organic compounds such as organobentonite, castor oil derivatives, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyethylene wax, etc.; among them, the rheological agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkaline expandable emulsion (HASE), and alkaline expandable emulsion (ASE). The amount of the rheology agent used is not particularly limited, but is generally 0.1 to 1% by weight.

The thickening agent in the additive can endow the polymer mixed solution with good thixotropy and proper consistency, thereby meeting the requirements of various aspects such as stability and application performance during production, storage and use, and the like, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, alkyldimethylamine oxides, fatty acid isopropylamide, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine; high molecular substances such as bentonite, artificial hectorite, micro-powder silica, colloidal aluminum, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, and the like; among them, the thickener is preferably bentonite or an acrylic acid-methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited, and is generally 0.1 to 1.5% by weight.

The leveling agent in the additive can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the leveling agent comprises any one or more of the following leveling agents: polyacrylates, silicone resins, and the like; among them, the leveling agent is preferably polyacrylate. The amount of the leveling agent to be used is not particularly limited, but is usually 0.5 to 1.5% by weight.

In the preparation process of the dynamic polymer, the auxiliary agents which can be added are preferably catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, plasticizers, foaming agents, flame retardants and dynamic regulators.

② the ② additive ② filler ② has ② the ② main ② functions ② of ② reducing ② the ② shrinkage ② rate ② of ② a ② formed ② product ②, ② improving ② the ② dimensional ② stability ②, ② surface ② smoothness ②, ② flatness ② or ② dullness ② of ② the ② product ②, ② regulating ② the ② viscosity ② of ② the ② polymer ②, ② meeting ② different ② performance ② requirements ② such ② as ② improving ② the ② impact ② strength ②, ② compression ② strength ②, ② hardness ②, ② rigidity ② and ② modulus ② of ② a ② polymer ② material ②, ② improving ② the ② wear ② resistance ②, ② heat ② deformation ② temperature ②, ② electrical ② conductivity ② and ② thermal ② conductivity ② and ② the ② like ②, ② improving ② the ② coloring ② effect ② of ② a ② pigment ②, ② endowing ② light ② stability ② and ② chemical ② corrosion ② resistance ②, ② playing ② a ② role ② of ② capacity ② increase ②, ② reducing ② the ② cost ② and ② improving ② the ② competitive ② capacity ② of ② the ② product ② in ② the ② market ②. ②

The filler which can be added is selected from any one or more of the following fillers: inorganic non-metal filler, metal filler and organic filler.

The inorganic non-metal filler which can be added comprises any one or any several of the following materials: calcium carbonate, china clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, carbon nanotubes, graphene oxide, molybdenum disulfide, slag, flue dust, wood powder and shell powder, diatomaceous earth, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, white mud, alkali mud, boric mud, (hollow) glass microbeads, foamed microspheres, glass powder, cement, glass fiber, carbon fiber, quartz fiber, carbon core boron fiber, titanium diboride fiber, calcium titanate fiber, carbon silicon fiber, ceramic fiber, whisker and the like.

The metal filler which can be added comprises, but is not limited to, any one or any several of the following: conductive metal fillers, metal particles, metal and alloy powders, carbon steel, stainless steel fibers, and the like.

The organic filler which can be added comprises but is not limited to any one or any several of the following: fur, natural rubber, cotton linter, hemp, jute, flax, asbestos, cellulose acetate, shellac, chitin, chitosan, lignin, starch, protein, enzyme, hormone, raw lacquer, wood flour, shell flour, glycogen, xylose, silk, rayon, vinylon, phenolic microbeads, resin microbeads, and the like.

The type of the added filler is not limited, and is determined mainly according to the required material properties, and calcium carbonate, barium sulfate, talc powder, carbon black, graphene, (hollow) glass beads, foamed microspheres, glass fibers, carbon fibers, metal powder, natural rubber, cotton linters, and resin beads are preferred, and the amount of the used filler is not particularly limited, and is generally 1 to 30 wt%.

In the preparation process of the dynamic polymer, the dynamic polymer can be prepared by mixing a certain proportion of raw materials by any suitable material mixing method known in the art, and the mixing can be in a batch, semi-continuous or continuous process; likewise, the dynamic polymer may be shaped in an alternative batch, semi-continuous or continuous process. The mixing method includes, but is not limited to, solution stirring mixing, melt stirring mixing, kneading, banburying, roll mixing, melt extrusion, ball milling, etc., wherein solution stirring mixing, melt stirring mixing and melt extrusion are preferred. Forms of energy supply during the material mixing process include, but are not limited to, heating, light, radiation, microwaves, ultrasound. The molding method includes, but is not limited to, extrusion molding, injection molding, compression molding, casting molding, calendaring molding, and casting molding.

In the preparation process of the dynamic polymer, other polymers which can be added, auxiliary agents which can be added and fillers which can be added to form a dynamic polymer composite system, but the additives are not all necessary.

The specific process for preparing dynamic polymers by stirring and mixing solutions is usually to mix the raw materials in dissolved or dispersed form in the respective solvents or in a common solvent in a reactor by stirring and mixing. Generally, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a suitable mould and placed at a temperature of 0-150 ℃, preferably 25-80 ℃ for 0-48h to obtain a polymer sample. In the process, the solvent can be selectively retained to prepare a polymer sample in the form of solution, emulsion, paste, gel and the like, or the solvent can be selectively removed to prepare a solid polymer sample in the form of film, block, foam and the like.

When the dynamic polymer is prepared by using the compound (IV) and the compound (V) as raw materials, it is usually necessary to add an initiator to a solvent as appropriate to initiate polymerization in a solution polymerization manner to obtain the dynamic polymer, or add a dispersant and an oil-soluble initiator to prepare a suspension to initiate polymerization in a suspension polymerization manner or a slurry polymerization manner to obtain the dynamic polymer, or add an initiator and an emulsifier to prepare an emulsion to initiate polymerization in an emulsion polymerization manner to obtain the dynamic polymer. The methods employed for solution polymerization, suspension polymerization, slurry polymerization and emulsion polymerization are all polymerization methods which are well known and widely used by those skilled in the art and can be adapted to the actual situation and will not be described in detail here.

The solvent used in the above preparation method should be selected according to the actual conditions of the reactants, the products, the reaction process, etc., and includes, but is not limited to, any one of the following solvents or a mixture of any several solvents: deionized water, acetonitrile, acetone, butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, chloroform, and dichloromethaneAlkane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, N-butyl acetate, trichloroethylene, mesitylene, dioxane, Tris buffer, citric acid buffer, acetic acid buffer, phosphoric acid buffer, etc.; deionized water, toluene, chloroform, dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, dimethylformamide, phosphoric acid buffer solution are preferred. In addition, the solvent may also be selected from oligomers, plasticizers, ionic liquids; the oligomer comprises but is not limited to polyvinyl acetate oligomer, poly (n-butyl acrylate) oligomer, liquid paraffin and the like; the plasticizer can be selected from the plasticizer category in the additive auxiliary agents, and the description is omitted; the ionic liquid is generally composed of an organic cation and an inorganic anion, and the cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphine ion, a 1, 3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion and the like; the anion is typically a halide, tetrafluoroborate, hexafluorophosphate, or CF₃SO₃ ^-、(CF3SO₂)₂N^-、C₃F₇COO^-、C₄F₉SO₃ ^-、CF₃COO^-、(CF₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₂F₅SO₂)₂N^-、SbF₆ ^-、AsF₆ ^-And the like. Wherein, when the dynamic polymer is prepared by using deionized water and is selected to be reserved, hydrogel can be obtained; preparing a dynamic polymer by using an organic solvent and selectively retaining the dynamic polymer to obtain organogel; preparing a dynamic polymer by utilizing the oligomer and obtaining an oligomer swelling gel when selecting to reserve the dynamic polymer; when the plasticizer is used for preparing the dynamic polymer and is selected to be reserved, the plasticizer swelling gel can be obtained; when the ionic liquid is used for preparing the dynamic polymer and the dynamic polymer is selected to be reserved, the ionic liquid swelling gel can be obtained.

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

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

When the dynamic polymer is produced by this method using the compound (IV) or the compound (V) as a raw material, it is usually necessary to initiate the polymerization by melt polymerization or gas phase polymerization by adding a small amount of an initiator as the case requires. The methods of melt polymerization and gas phase polymerization, which are well known and widely used by those skilled in the art, can be adjusted according to the actual conditions and will not be described in detail herein.

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

In the preparation process of the dynamic polymer, the component selection and the formula proportion of the selected organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) can be flexibly grasped, but the reasonable design and combination are carried out according to the target material performance, the structure of the selected compound, the number of the contained reactive groups and the molecular weight. Wherein the organoboron compound (I), the silicon-containing compound (II), the compound (III), the compound (IV) and the compound (V) are added so as to ensure that the molar equivalent ratio of the functional groups and/or other reactive groups in the reactant system is in an appropriate range. The molar equivalent ratio of the organoboron compound (I), the silicon-containing compound (II) or the organoborate group contained in the compound (III) to the silicon hydroxyl group and/or the silicon hydroxyl group precursor functional group 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 silicon-containing compound (II) and the compound (III) 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 silicon-containing compound (II) and the compound (III) deviates from 1:1, a dynamic polymer having good dynamic properties can be obtained. Similarly, when the compound (IV) or the compound (V) is used as a reaction component for preparing a dynamic polymer, the molar equivalent ratio of the other reactive groups in the reactant system is also in an appropriate range, and the molar equivalent ratio of the other reactive groups to be subjected to the polymerization/crosslinking reaction is preferably in a range of 0.1 to 10, more preferably in a range of 0.3 to 3, and still more preferably in a range of 0.8 to 1.2. In the actual preparation process, the skilled person can adjust the process according to the actual needs.

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

The dynamic polymer has wide-range adjustable performance and wide application prospect, and shows remarkable application effect in the fields of military aerospace equipment, functional coatings, biomedicine, biomedical materials, energy sources, buildings, bionics, intelligent materials and the like.

For example, by utilizing the dilatancy of the dynamic polymer, the polymer can be applied to the aspects of oil extraction of oil wells, fuel explosion prevention and the like; the polymer material can dissipate a large amount of energy to play a role in damping when being vibrated, thereby effectively easing the vibration of a vibrator; the stress responsiveness of the dynamic polymer can be utilized as an energy-absorbing buffer material, and the energy-absorbing buffer material can be applied to the aspects of buffer packaging materials, sports protection products, impact protection products, military and police protection materials and the like, so that the vibration and impact of articles or human bodies under the action of external force, including shock waves generated by explosion and the like, can be reduced, the energy-absorbing buffer material can also be used as a shape memory material, and when the external force is removed, the deformation of the material generated in the loading process can be recovered; the stress-sensitive polymer material is prepared through the dynamic reversibility and stress rate dependence of the dynamic polymer, and part of the stress-sensitive polymer material can be applied to preparing toys and body-building materials with the magic effect of creep property and high elastic conversion, can also be used for preparing speed lockers of roads and bridges, and can also be used for manufacturing anti-seismic shear plates or cyclic stress bearing tools, or can be used for manufacturing stress monitoring sensors.

For another example, the self-repairing property of the dynamic polymer is fully utilized, so that the adhesive with the self-repairing function can be prepared, and the adhesive can be applied to the adhesion of various materials and can also be used as a bulletproof glass interlayer adhesive; the preparation method can also be used for preparing polymer plugging glue, sealing plugs, sealing rings and other sealing elements which have good plasticity and can be recovered and repaired; based on the dynamic reversibility of the organic boric acid silicon ester bond and the side hydrogen bond, the scratch-resistant coating with the self-repairing function can be designed and prepared, so that the service life of the coating is prolonged, and long-acting anticorrosion protection on a matrix material is realized; through proper component selection and formula design, the polymer gasket or the polymer plate with the self-repairing function can be prepared, so that the principle of organism injury healing can be simulated, the material can carry out self-healing on internal or external injuries, hidden dangers are eliminated, the service life of the material is prolonged, and the material has great application potential in the fields of military industry, aerospace, electronics, bionics and the like.

For example, when the organic boric acid silicone ester bond and the supermolecule hydrogen bond are used as sacrificial bonds, the organic boric acid silicone ester bond and the supermolecule hydrogen bond can absorb a large amount of energy under the action of external force to endow polymer materials with excellent toughness, so that polymer films, fibers or plates with excellent toughness can be obtained, and the organic boric acid silicone ester polymer can be widely applied to the fields of military affairs, spaceflight, sports, energy sources, buildings and the like.

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

Example 1

Preparing a dynamic polymer with a single hybrid crosslinking network by using a macromolecular organic boron compound (I) and a small molecular silicon-containing compound (II).

Adding 20g of acrylamide-phenylboronic acid-carbamate copolymer (a) (prepared by taking methyl isocyanate and N- (2-hydroxyethyl) acrylamide as raw materials to react to prepare a carbamate monomer, further taking AIBN as an initiator, and performing RAFT free radical polymerization on the acrylamide, the 3-acrylamidophenylboronic acid and the carbamate monomer), 200ml of deionized water/THF mixed solvent, heating to 50 ℃, stirring and dissolving, slowly adding 2.8g of 1,1,3,3,5,5,7, 7-octamethyl-1, 7-tetrasiloxane diol (b), stirring and mixing for 30min, adding 2ml of triethylamine, and continuing to stir and react for 2h at 50 ℃. Then adding 1.0g of sodium dodecyl benzene sulfonate, 0.6g of bentonite, 0.3g of stearic acid and 0.3g of oleic acid, adding 0.3g of organobentonite, 0.3g of polydimethylsiloxane, 0.3g of dibutyltin dilaurate and 30mg of light stabilizer 770, heating, stirring and uniformly mixing to obtain a milky white liquid with a certain viscosity, and utilizing the dilatancy of the milky white liquid, the milky white liquid can be used for coating or impregnating fabrics to prepare impact protective clothing or sports pads.

Example 2

Preparing a dynamic polymer with a single hybrid crosslinking network by using a macromolecular silicon-containing compound (II) and a small molecular organic boron compound (I).

Adding 7.5g of boric acid compound (b) (prepared by taking 2-aminomethyl phenylboronic acid 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 ℃, stirring and dissolving, then dropwise adding a small amount of 20% acetic acid aqueous solution, slowly adding 30g of silane modified polypropylene oxide copolymer (a) (prepared by taking propylene glycol, propylene oxide and N- (2-ethylene oxide methyl) carbamate as raw materials and boron trifluoride diethyl etherate as a catalyst, synthesizing a propylene oxide copolymer with carbamate groups at side groups through cationic ring-opening polymerization, respectively reacting with 4, 4' -diphenylmethane diisocyanate and 3-aminopropyltrimethoxysilane to obtain a final product), stirring and mixing for 30min, adding 2ml of triethylamine, and continuously stirring and reacting for 6h under the protection of nitrogen at the temperature of 80 ℃, pouring the reactant into a proper mould, placing the mould in a vacuum oven at the temperature of 60 ℃ for 24h, and then cooling to room temperature and placing for 30min to obtain the polymer elastomer. The obtained polymer elastomer has low surface hardness and good rebound resilience, and can be extended in a large range under the action of external force (the elongation at break can reach 2000%). In this example, the obtained polymer sample was used as a sealant and applied to sealing of building caulking and sealing treatment of electronic components.

Example 3

And (3) preparing the dynamic polymer with the single hybrid cross-linked network by using the macromolecular compound (V), the small molecular compound (V) and the small molecular compound (IV).

Weighing 25g of polyethylene glycol copolymer (a) (which is synthesized by taking ethylene glycol, ethylene oxide and 2-methyl-2-propyl [3- (2-ethylene oxide) propyl ] carbamate as raw materials and boron trifluoride diethyl etherate as a catalyst through cationic ring-opening polymerization), heating to 110 ℃ to remove water for 1h, then adding 14g of toluene diisocyanate (b), reacting for 3h under the protection of nitrogen at 80 ℃, then cooling to 60 ℃, adding 2.3g of chain extender dimethylolpropionic acid (c), 1.5g of triethylamine, 10g of acetone and 0.12g of stannous octoate, refluxing for reaction for 2h, then adding 4.5g of organic boron silicon ester compound (d) (which takes 4-aminobenzene boric acid and dimethyl methoxy-3- (2-aminoethylthio) propyl silane as raw materials), prepared by condensation reaction) as a cross-linking agent, continuously reacting for 1h, pouring the polymer solution into a proper mould for tape casting to form a film, drying at room temperature for 24h to obtain a hybrid cross-linked polymer film, cutting the hybrid cross-linked polymer film into dumbbell-shaped sample strips with the sizes of 80.0 multiplied by 10.0 multiplied by (0.08 +/-0.02), and performing tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 3.13 +/-0.64 MPa, the tensile modulus is 5.35 +/-1.68 MPa, and the elongation at break is 1034 +/-255%. The film tearing performance test is carried out on a right-angle non-notch standard test sample prepared according to the QB/T1130-91 plastic right-angle tearing performance test method, and the transverse tearing strength and the longitudinal tearing strength of the sample are respectively 6.91 +/-1.79 MPa and 6.33 +/-2.04 MPa. The prepared hybrid cross-linked polymer film has certain mechanical strength and excellent tensile toughness. In addition, after the film sample is pulled apart, the film sample is placed in a mold at 50 ℃ and applied with a certain pressure for 4 hours, cracks on the film disappear, and the film can be reshaped and has a self-repairing effect. The polymer film can be applied to the medical and health field as medical gloves or medical garment fabrics, and can also be used as sports or special functional shoe fabrics and lining materials.

Example 4

Preparing a dynamic polymer with a single hybrid cross-linked network by using a small molecular organic boron compound (I), a small molecular silicon-containing compound (II) and a small molecular compound (V).

Weighing 25ml of resorcinol type epoxy resin (a), adding the resorcinol type epoxy resin (a) into a three-neck flask, heating to 60 ℃, introducing nitrogen, keeping the temperature for 1h, adding 9.62g of 4-aminophenylboronic acid pinacol ester (b), 7.02g of 3-aminopropyl trimethoxy silane (c) and 2.48g of 1- (6-aminohexyl) -3-ethylurea (d) (prepared by taking hexamethylene diamine and ethyl isocyanate as raw materials for reaction), stirring for 3h, dropwise adding a small amount of 20% acetic acid aqueous solution, continuing to stir for reaction for 30min, then adding 0.5g of triethylamine, continuing to react for 2h, then sequentially adding 3.2g of glass microfiber, 0.14g of silane coupling agent KH550 and 0.14g of sodium dodecyl benzene sulfonate, stirring for 10min, then adding 0.07g of bentonite, uniformly mixing, and continuing to react under a stirring state. In the reaction process, the viscosity of the liquid continuously rises, when the viscosity rises to a certain stage, a yellow viscous polymer sample is poured into a proper mould, the mould is placed in a vacuum oven at 80 ℃ for continuous reaction for 5 hours, then the reaction is cooled to room temperature and placed for 30 minutes, and finally a hard epoxy resin curing material is obtained, wherein the hard epoxy resin curing material has certain surface hardness, after the hard epoxy resin curing material is broken off, the glass microfiber is observed to be uniformly distributed in a matrix, the section is attached and placed in an oven at 120 ℃ for 12 hours (the section can be slightly wetted in the process), the material can be bonded again, and compared with the traditional epoxy resin curing material, the material has recyclability.

Example 5

And (3) preparing the dynamic polymer with the single hybrid cross-linked network by using the small molecular compound (IV) and the small molecular compound (V).

120ml of an anhydrous tetrahydrofuran solvent was charged into a dry and clean reaction flask, and 6.38g of a silyl borate compound (a) (obtained by condensation reaction of 1-aminoethylboronic acid and 3-aminopropyldimethylethoxysilane) and 12.75g of an amino compound (c) (obtained by reaction of a triallylamine and mercaptoethylamine with a fixed amount of methyl isocyanate after an intermediate product was obtained by thiol-olefin click addition reaction) were added thereto and dissolved by stirring, and 13.44g of decane-1, 10-diisocyanate (b) was added dropwise thereto and reacted at 60 ℃ for 3 hours by stirring and mixing. After the reaction is finished, the solvent is removed by vacuum filtration to obtain a white solid of the dynamic polymer. The obtained polymer sample has a soft surface and can be used as a functional plugging adhesive.

Example 6

Respectively weighing 18g of chlorosilane-terminated polybutadiene (a) (prepared by taking hydroxyl-terminated 1, 3-polybutadiene and tetrachlorosilane as raw materials, toluene as a solvent and triethylamine as a catalyst to absorb HCl generated by the reaction), 4.78g of organic boron compound (b) (prepared by taking AIBN as an initiator and triethylamine as a catalyst to perform a thiol-ene click reaction on vinyl boric acid and 1, 4-butanedithiol), 2.5g of boric acid compound (c) (prepared by taking AIBN as an initiator and triethylamine as a catalyst to perform a thiol-ene click reaction on vinyl boric acid and N- [ (2-mercaptoethyl) carbamoyl ] propionamide), adding 60ml of toluene solvent, introducing nitrogen for protection, heating to 80 ℃, stirring for dissolution, and then reacting for 8 hours under a reflux condition. The solvent was then distilled off under reduced pressure and the product was cooled to room temperature, giving a polybutadiene sample in the rubbery state. The polymer sample has certain flexibility and good formability, and can be formed according to moulds in different shapes. The polymer sample can creep and deform greatly at a slow drawing speed, and after the broken polymer sample is recovered, the polymer sample can be re-shaped after being placed in a mould at 50 ℃ for 3-4 h. In this embodiment, the polymer sample can be used as a functional sealant or plugging glue, which can exhibit good dimensional adaptability, self-repairability and toughness.

Example 7

And (3) preparing the dynamic polymer with the single hybrid cross-linked network by using the macromolecular compound (V), the small molecular compound (IV) and the small molecular compound (V).

40ml of methyl hydrogen silicone oil (a) (with the molecular weight of about 20,000), 6.46g of silicon borate compound (b) (prepared by taking 5-hexenylboronic acid and propenyl dimethylchlorosilane as raw materials and triethylamine as a catalyst and reacting at the temperature of 80 ℃), 3.36g of carbamate compound (c) (prepared by taking ethyl isocyanate and propylene glycol monoallyl ether as raw materials) and 2ml of 1% Pt (dvs) -xylene solution as a catalyst are added, the mixture is heated to 80 ℃ and reacted for 24 hours under the protection of nitrogen, and finally a colloidal polymer sample can be obtained, and can be slowly extended under the action of external tensile stress to obtain the super-stretching effect (the elongation at break can reach 3000%). In this embodiment, the prepared polymer sample can be used as an interlayer adhesive of bulletproof glass, and has the effect of dissipating stress under the action of impact force.

Example 8

Taking a certain amount of organic boron compound (a) with a hyperbranched structure (taking diethanolamine and methyl acrylate as raw materials to synthesize 3- (bis (2-hydroxyethyl) amino) methyl propionate, reacting the organic boron compound (a) with trimethylolpropane in a dropwise manner under the catalysis condition of p-toluenesulfonic acid at 115 ℃ to prepare a first-stage intermediate product, then reacting the first-stage intermediate product with 3- (bis (2-hydroxyethyl) amino) methyl propionate to prepare a second-stage intermediate product, carrying out hydroxyl end capping by using 3-propylene isocyanate, and then carrying out thiol-ene click reaction with quantitative 4-mercaptophenylboronic acid to prepare a final product) to be dissolved in a trichloromethane solvent to prepare a 0.1mol/L solution; meanwhile, a certain amount of silane compound (b) (prepared by condensation reaction of 3-aminopropylmethyldimethoxysilane and adipic acid by using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts) is taken and dissolved in a trichloromethane solvent to prepare a solution with the concentration of 0.6 mol/L. Adding 20ml of organic boron compound solution into a dry clean flask, dropwise adding a small amount of 20% acetic acid aqueous solution, uniformly stirring at room temperature, heating to 80 ℃, dropwise adding 20ml of silane solution, reacting for 30min, then adding 2ml of triethylamine, and continuously stirring and reacting for 4h at 80 ℃. After the reaction, the apparent viscosity of the polymer fluid was measured by a rotational viscometer at 25 ℃ with a constant shear rate of 0.1s^-1The apparent viscosity of the polymer fluid was found to be 48,760 mPas. Maximum elastic modulus G 'of Polymer fluids Using a rotational rheometer'_maxAnd minimum modulus of elasticity G'_minTesting is carried out, wherein the testing temperature is 25 ℃, the testing frequency range is 0.1-100 rad/s, and the maximum elastic modulus G 'of the polymer fluid is measured'_maxIs 4.92 multiplied by 10⁴Pa, minimum elastic modulus G'_minThe pressure is 21.46Pa, the polymer fluid can show sensitive dilatancy under the action of stress/strain, and the polymer fluid can be applied to textiles to be made into an impact-resistant energy-absorbing material.

Example 9

Preparing a dynamic polymer with a single hybrid crosslinking network by using a macromolecular organic boron compound (I), a macromolecular silicon-containing compound (II) and a small molecular compound (V).

Taking a certain amount of dendritic organic boron compound (a) (2, 2-dimethoxy-acetophenone (DMPA) as a photoinitiator, ultraviolet light as a light source, vinyl boric acid and 1, 2-ethanedithiol are subjected to mercaptan-olefin click addition reaction to prepare mercaptoboric acid, DMPA is taken as a photoinitiator, ultraviolet light is taken as a light source, triallylamine and 1, 2-ethanedithiol are subjected to mercaptan-olefin click addition reaction to prepare a primary intermediate product, then the primary intermediate product and triallylamine are subjected to mercaptan-olefin click addition reaction to prepare a secondary intermediate product, then the secondary intermediate product and 1, 2-ethanedithiol are subjected to mercaptan-olefin click addition reaction to prepare a tertiary intermediate product, then the tertiary intermediate product and triallylamine are subjected to reaction to prepare a quaternary intermediate product, and finally the quaternary intermediate product, mercaptoboric acid and 1, 2-ethanedithiol are subjected to mercaptan-olefin click addition reaction to prepare a final product) are dissolved in a toluene solvent to prepare 0.01mol L, adding 0.2mg of BHT antioxidant; a certain amount of dimethylhydroxysilicone oil (b) (molecular weight about 4000) is taken and heated to be dissolved in a toluene solvent to prepare a solution of 0.2 mol/L. Respectively taking 20ml of organic boron compound solution and silicone oil solution, adding 0.2g of triethylamine, stirring uniformly, reacting for 2H under the condition of nitrogen protection at 60 ℃, then adding 0.47g of compound (c) (prepared by reacting 2-amino-4 (1H) -pyrimidone and 1, 6-hexamethylene diisocyanate at 100 ℃) and continuing to react for 1H under the condition of nitrogen protection. The polymer solution was then poured into a suitable mold, placed in an oven at 50 ℃ for 24h for drying and further reaction to give a polymer sample in the form of a transparent film. The specimen was cut into a dumbbell-shaped specimen having a size of 80.0X 10.0X (0.08. + -. 0.02) mm, and subjected to a tensile test using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 3.24. + -. 0.85MPa, a tensile modulus of 6.01. + -. 1.54MPa and an elongation at break of 1128. + -. 344%. The film tearing performance test is carried out on a right-angle non-notch standard test sample prepared according to the QB/T1130-91 plastic right-angle tearing performance test method, and the transverse tearing strength and the longitudinal tearing strength of the sample are respectively 6.85 +/-1.20 MPa and 5.93 +/-1.34 MPa. The obtained polymer film is soft and tough in texture, has certain tensile strength and tensile modulus, and also shows good tensile toughness which other crosslinked films do not have. In addition, after the film sample is pulled apart, the film sample is placed in a die at 50 ℃ and applied with a certain pressure for 3-4 hours, cracks on the film disappear, and the film can be reshaped, so that a self-repairing effect is embodied. In the actual use process, the damaged and broken polymer film can be recycled and reused after sample preparation, and the cross-linked polymer film can be widely applied to the fields of military affairs, aviation, biomedicine and the like as a functional film product, can be prefabricated into an inflatable cushion buffer packaging material for use, and plays a role in buffer protection of the packaged product.

Example 10

Preparing a dynamic polymer with a double cross-linked network by using a macromolecular compound (V), a macromolecular organic boron compound (I) and a small molecular silicon-containing compound (II), wherein the first network is dynamic covalent cross-linking, and the second network is supermolecule hydrogen bond cross-linking.

Adding 100ml of tetrahydrofuran solvent and 15g of phenylboronic acid-terminated polytetrahydrofuran (b) (prepared by taking 3-aminophenylboronic acid as a raw material and carrying out a alkylation reaction with dibromo-terminated polytetrahydrofuran (with the molecular weight of about 1000)) into a dry and clean reaction bottle, adding a small amount of 20% acetic acid aqueous solution while stirring, uniformly mixing, then sequentially and slowly adding 1.85g of 1,1,3,3,5, 5-hexaethoxy-1, 3, 5-trisilacyclohexane (c) and 4.16g of tetradecyl-1, 11-dichlorohexasiloxane (d), stirring to fully and uniformly mix the components, adding 2ml of triethylamine, reacting at 80 ℃ for 4 hours to obtain a polymer fluid with a certain viscosity, then adding 9.5g of the compound (a) into the reaction bottle (after the polyetheramine with the molecular weight of about 800 is terminated by methylene diisocyanate, then pentaerythritol is used for blocking, and then the reaction product is sequentially reacted with 1, 6-hexamethylene diisocyanate and 1- (2-hydroxyethyl) -2-imidazolidinone to prepare a final product), and the reaction product is continuously reacted for 2 hours under the stirring state. After the reaction was complete, the apparent viscosity of the polymer fluid was measured using a rotational viscometer at 25 ℃ with a constant shear rate of 0.1s^-1The apparent viscosity of the polymer fluid was measured to be 39,520 mPas. Maximum elastic modulus G 'of Polymer fluids Using a rotational rheometer'_maxAnd minimum modulus of elasticity G'_minTesting is carried out, wherein the testing temperature is 25 ℃, the testing frequency range is 0.1-100 rad/s, and the maximum elastic modulus G 'of the polymer fluid is measured'_maxIs 2.96 multiplied by 10⁴Pa, minimum elastic modulus G'_minIt was 28.76 Pa. Dynamic polymer fluids exhibit significant dynamic properties and "shear thickening" properties and can be applied to textiles to make impact resistant protective articles, for example, for use as athletic apparel or as athletic padding.

Example 11

Preparing a dynamic polymer with a double cross-linked network by using a small molecular organic boron compound (I), a small molecular silicon-containing compound (II) and a macromolecular compound (V), wherein the first network is dynamic covalent cross-linking, and the second network is supermolecule hydrogen bond cross-linking.

Dissolving an organic boron compound (a) (which is prepared by taking 1-hydroxyboron heterocyclic propylene as a raw material and performing addition reaction on the raw material and hydrobromic acid to prepare 2-bromo-1-hydroxyboron heterocyclic propane, taking 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine and 2-aminoethanethiol as raw materials, AIBN as an initiator and triethylamine as a catalyst, performing a thiol-ene click reaction to prepare an intermediate product, and performing a alkylation reaction on the intermediate product and 2-bromo-1-hydroxyboron heterocyclic propane) in a tetrahydrofuran solvent to prepare a 0.5mol/L solution; dissolving a certain amount of silicon-containing compound (b) (prepared by taking trimethylolpropane tris (3-mercaptopropionate) and 1-chloro-vinyl-silacyclobutane as raw materials, AIBN as an initiator and triethylamine as a catalyst through a thiol-ene click reaction) in a tetrahydrofuran solvent to prepare a 0.5mol/L solution. Adding 20ml of prepared organic boron compound solution into a dry and clean beaker, dropwise adding a small amount of 20% acetic acid aqueous solution, dropwise adding 20ml of silicon-containing compound solution under the stirring state, uniformly stirring at 50 ℃, dropwise adding 2ml of triethylamine, continuously reacting for 4 hours to form a first network, then adding 2.4g of modified polycyclooctene compound (c) (taking cyclooctadiene and m-chloroperoxybenzoic acid as raw materials and acetonitrile as a solvent, hydrolyzing in an acidic solution to obtain 5-cyclooctene-1, 2-diol, mixing the 5-cyclooctene-1, 2-diol with cyclooctene, preparing polycyclooctene with side base hydroxyl groups under the action of Grubbs catalyst, reacting with ethoxycarbonyl isocyanate to obtain a final product, completely dissolving the reactants by stirring, and reacting for 2 hours at 50 ℃ to form a second network. And then pouring the reaction liquid into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 24h for further reaction and drying, cooling to room temperature, and standing for 30min to finally obtain a colloidal polymer material, wherein the sample has certain elasticity and toughness and can be extended in a larger range. The sample is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm, and a tensile test is carried out by a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 1.97 +/-0.75 MPa, the tensile modulus is 3.02 +/-1.06 MPa, and the elongation at break is 678 +/-166%. In addition, the prepared product has good plasticity, can be placed in moulds of different shapes according to actual needs, and can be molded into polymer products of different shapes according to the moulds by slightly applying certain stress under a certain temperature condition. In this embodiment, the polymer may be used in the form of a resilient washer and a resilient gasket.

Example 12

Preparing a dynamic polymer with a double cross-linked network by using a macromolecular organic boron compound (I), a macromolecular silicon-containing compound (II) and a macromolecular compound (V), wherein the first network is dynamic covalent cross-linking, and the second network is supermolecule hydrogen bond cross-linking.

Weighing 4.1g of boric acid-terminated four-arm compound (a) (prepared by performing alkylation reaction on 2-aminomethyl phenylboronic acid and tetrabromo-quaternary amyl alcohol) and dissolving in 80ml of DMF/THF mixed solvent, uniformly mixing under a stirring state, slowly adding 9.6ml of hydroxyl-terminated methylphenyl silicone oil (b) (with the molecular weight of about 12,000), stirring and mixing for 30min, adding 2ml of triethylamine, and reacting for 1h under the nitrogen protection reflux condition; then 5ml of modified silicone oil (c) (which is prepared by taking cyanuric acid and 6-chloro-1-hexene as raw materials, reacting under the catalysis of potassium carbonate to obtain an olefin monomer containing a hydrogen bond group, and then carrying out hydrosilylation with methyl hydrogen-containing silicone oil with the molecular weight of 20,000 under the catalysis of Pt) is added to continue to react for 4 hours under the protection of nitrogen. And in the reaction process, the viscosity of the solution is continuously increased, after the reaction is finished, the polymer solution is poured into a proper mould, the mould is placed in a vacuum oven at 80 ℃ for 24 hours to remove the solvent, then the mould is cooled to room temperature and placed for 30 minutes, and finally a massive milky yellow polymer solid sample in a hard colloidal state is obtained. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile testing machine at a tensile rate of 10mm/min to obtain a specimen having a tensile strength of 4.78. + -. 2.03MPa and a tensile modulus of 8.97. + -. 2.46 MPa. The polymer sample can show a certain stress response effect along with the change of external force, and can be used as a stress monitoring sensor.

Example 13

Preparing a dynamic polymer with a double cross-linked network by using a macromolecular organic boron compound (I), a small molecular silicon-containing compound (II) and a macromolecular silicon-containing compound (II), wherein the first network is dynamic covalent cross-linking and supermolecule hydrogen bond cross-linking, and the second network is dynamic covalent cross-linking.

Weighing 6.50g of acrylamide-boric acid copolymer (a) (prepared by taking 1-amino ethyl diisopropyl borate and acryloyl chloride as raw materials to react to prepare a boric acid ester acrylamide monomer 1; prepared by taking isocyanate ethyl acrylate and ethylamine as raw materials to react to prepare a monomer 2; and prepared by carrying out free radical polymerization on the monomer 1, the monomer 2 and N, N-dimethylacrylamide to obtain a final product), adding 40ml of deionized water, continuously stirring and dissolving at 50 ℃, and after complete dissolution, dropwise adding a small amount of 1mol/L NaOH solution into the mixture; 2.80g of silane-terminated polyethylene glycol (b) (prepared by reacting isocyanatopropyltrimethoxysilane with polyethylene glycol 400) is weighed and slowly added into the acrylamide-boric acid copolymer solution, the mixture is dissolved and mixed by continuous stirring in the process, and after the mixture is completely dissolved, the mixture is placed in a 60 ℃ water bath to be heated and reacted for 3 hours to obtain the first network gel. Weighing a certain amount of acrylamide-boric acid copolymer (c) (4-hydroxyphenylboronic acid and acryloyl chloride are used as raw materials to react to prepare a boric acid acrylate monomer, and then the boric acid acrylate monomer and N, N-dimethylacrylamide are subjected to free radical polymerization to obtain a final product) and dissolving the final product in deionized water to prepare the acrylic acid acrylate polymer0.4mol/L solution; meanwhile, a certain amount of acrylamide-silane copolymer (d) (prepared by taking 2-acrylic acid-3- (diethoxymethylsilane) propyl ester as a raw material and AIBN as an initiator and carrying out free radical polymerization with N, N-dimethylacrylamide) is weighed and dissolved in deionized water to prepare 0.5mol/L solution, and 20ml of each of the two copolymer solutions are uniformly mixed. Swelling the prepared first network gel in a copolymer mixed solution, performing ultrasonic treatment for 5min, and adding 1.6g of Fe subjected to surface modification by using a silane coupling agent A151₃O₄The particles and 1.0g bentonite are treated by ultrasonic treatment for 1min to enable Fe₃O₄The particles are uniformly dispersed in the solution, then a small amount of 1mol/L NaOH solution is added dropwise, and the solution is placed in a thermostatic water bath at the temperature of 60 ℃ for reaction for 2 hours. After the reaction is finished, the double-network hydrogel dispersed with the magnetic particles is obtained. The polymer samples were viscous at the surface, elastic and compressible, and could be stretched to some extent. After scratching the surface of the polymer by using a blade, attaching the scratched part, and placing the polymer in a 60 ℃ oven for 4-6 hours, wherein the scratched part can be self-repaired. The polymer gel can embody the functional characteristics of self-repairing, pH response and the like. In the embodiment, the prepared magnetic gel can show various deformations such as elongation, contraction or bending under the action of a magnetic field, the network structure of the gel is not damaged in the process due to the excellent toughness of the gel, and the dynamic polymer gel can be widely applied to the fields of targeted drug release, cell separation and labeling, protein adsorption and separation and the like due to the unique responsiveness, flexibility and permeability of the dynamic polymer gel.

Example 14

And (3) preparing the dynamic polymer with a double cross-linked network by utilizing the macromolecular compound (III) and the macromolecular compound (V), wherein the first network is dynamic covalent cross-linking, and the second network is supermolecule hydrogen bond cross-linking.

Adding 25ml of organic boric acid-silane modified silicone oil (a) (prepared by taking methyl mercapto silicone oil with the molecular weight of about 60,000, dimethyl vinyl borate and methyl vinyl diethoxy silane as raw materials and DMPA as a photoinitiator through a thiol-ene click reaction under the condition of ultraviolet irradiation) into a three-neck flask, heating to 80 ℃, adding a small amount of deionized water, dropwise adding 2ml of triethylamine, carrying out polymerization reaction for 3h under the stirring state to form a first network, adding 20ml of modified silicone oil (b) (prepared by taking ethanethiol and isocyanate ethyl acrylate as raw materials and carrying out reaction to obtain an acrylate monomer containing thiocarbamate groups, and then carrying out reaction with methyl mercapto silicone oil with the molecular weight of about 60,000 by taking DMPA as a photoinitiator and carrying out thiol-ene click reaction under the ultraviolet irradiation condition) for 2h under the condition of 80 ℃. During the polymerization, the viscosity of the silicone oil gradually rises, and when the viscosity reaches a certain value, the silicone oil is poured into a suitable mold, and the mold is placed in a vacuum oven at 80 ℃ for continuous reaction for 24 hours, and then the silicone oil is cooled to room temperature and placed for 30 minutes, and finally a rubbery transparent polymer sample is obtained, which has certain surface elasticity and can be subjected to tensile extension in a large range (the elongation at break can reach 5000%). In the embodiment, the dynamic bond in the dynamic polymer is particularly resistant to hydrolysis, can keep a transparent state for a long time, and can be used as a super hot melt adhesive with self-repairing property or a bulletproof glass interlayer adhesive.

Example 15

Preparing a dynamic polymer with a single hybrid crosslinking network by using the macromolecular organic boron compound (I) and the macromolecular silicon-containing compound (II).

Adding 20g of acrylate copolymer (a) (4-hydroxymethyl pinacol borate reacts with acryloyl chloride to prepare phenylboronate acrylate monomer 1), reacting isocyanate ethyl acrylate with ethylamine to prepare acrylate monomer 2 containing urea bonds, using AIBN as an initiator, performing free radical polymerization on the phenylboronate acrylate monomer 1, the acrylate monomer 2 and methyl methacrylate to obtain 200ml of ethyl acetate solvent, heating to 50 ℃, stirring and dissolving, dropwise adding a small amount of 20% acetic acid aqueous solution, slowly adding 5g of silane modified polycaprolactone (b) (using allyl alcohol as an initiator and stannous octoate as a catalyst, initiating epsilon-caprolactone ring-opening polymerization to obtain olefin single-terminated polycaprolactone, esterifying the olefin single-terminated polycaprolactone with acrylic acid to obtain olefin double-terminated polycaprolactone, and reacting the olefin single-terminated polycaprolactone with gamma-mercaptopropyl trimethoxysilane by using AIBN as an initiator, triethylamine is used as a catalyst, a final product is obtained through a thiol-ene click reaction), after stirring and mixing for 30min, 2ml of triethylamine is added, and stirring and reaction are continued for 3h at the temperature of 80 ℃. After the reaction is finished, pouring the polymer solution into a proper mould, putting the sample into an oven at 80 ℃ for 24h to remove the solvent, cooling to room temperature, and standing for 30min to finally obtain a hard solid polymer sample with certain hardness and surface gloss. The sample was prepared into a dumbbell-shaped sample bar having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile tester at a tensile rate of 50mm/min to obtain a sample having a tensile strength of 3.51. + -. 1.16MPa and a tensile modulus of 5.87. + -. 2.24 MPa. After the polymer sample is pulled apart, the polymer sample is placed in a mold at 80 ℃ and applied for 4-6h under certain pressure (the section can be selected to be slightly wetted in the process), and the sample can be bonded and molded again and has self-repairing property. In the actual use process, the plate can be used as a recyclable plate.

Example 16

Preparing a dynamic polymer with a double cross-linked network by using a macromolecular organic boron compound (I), a macromolecular silicon-containing compound (II) and a small molecular compound (V), wherein the first network is supramolecular hydrogen bond cross-linked, and the second network is dynamic covalent cross-linked.

200ml of ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate is weighed in a dry and clean three-neck flask, heated to 110 ℃ after nitrogen protection, dissolved and dehydrated for 1h, then added with 10.57g N-isopropyl acrylamide (a) and 6.32g of compound (b) (prepared by taking isocyanate ethyl acrylate and 2-aminopyridine as raw materials for reaction), heated to 80 ℃ and dissolved and mixed uniformly, then added with 0.08g of ammonium persulfate, and reacted for 5h under the nitrogen protection condition to obtain a first network. 10g of vinylpyrrolidone-boric acid copolymer (c) (obtained by RAFT radical polymerization using AIBN as an initiator and vinylpyrrolidone and 3-acrylamidophenylboronic acid as raw materials) was added dropwise to the mixture, a small amount of 20% acetic acid aqueous solution was added dropwise thereto, 8g of vinylpyrrolidone-silane copolymer (d) (obtained by radical polymerization using 2-propenoic acid-3- (diethoxymethylsilane) propyl ester as a raw material and AIBN as an initiator) was added thereto, and the resultant was reacted with vinylpyrrolidone to obtain 2.16g of graphene powder and 0.1g of sodium dodecylbenzenesulfonate, and after stirring at 60 ℃ for 30 minutes, 0.04g of bentonite was added thereto, and the mixture was heated to 80 ℃ to carry out a stirring and mixing reaction, and after a mixing reaction for 3 hours, a second network was obtained. Pouring the viscous polymer solution into a proper mould, placing the mould in a vacuum oven at 50 ℃ for drying for 24h, then cooling to room temperature and placing for 30min to finally obtain a graphene-dispersed double-network ionic liquid gel polymer sample, and pressing the surface of the sample by fingers, wherein the sample can show certain elasticity and can be stretched and extended in a larger range. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile testing machine at a tensile rate of 50mm/min, whereby the tensile strength of the specimen was 1.83. + -. 0.66MPa, the tensile modulus was 3.69. + -. 1.42MPa, and the elongation at break was 753. + -. 215%. The polymer sample in the embodiment has good self-repairing performance, after the polymer sample is cut off by a knife, the section is slightly pressed for fitting (the section can be optionally slightly wetted in the process), and the section can be bonded again after being placed in a mold at 60 ℃ and heated for 4-6 h. The dynamic polymer sample in this embodiment can use it as the compound intelligent heat conduction material of graphite alkene, and based on the strong heat conductivity of graphite alkene, be favorable to carrying out the quick restoration of inside small damage under the heating state.

Example 17

Respectively weighing 12.4g of boric acid ester modified polybutadiene (a) (prepared by taking amino-terminated 1, 3-polybutadiene and diisopropyl (bromomethyl) borate as raw materials, preparing an intermediate product through a alkylation reaction, then reacting with 3-amino-N- (2-mercaptoethyl) propionamide through a mercaptan-olefin click addition reaction under the condition of ultraviolet irradiation by taking DMPA as a photoinitiator), 3.8g of silicon dioxide (b) with silicon hydroxyl on the surface, adding 40ml of benzene solvent, uniformly mixing the mixture by stirring at 50 ℃, adding 20mg of sodium dodecyl benzene sulfonate and 10mg of bentonite, heating to 70 ℃, continuously reacting for 4 hours, placing the product in a proper mould after the reaction is finished, and drying in a vacuum oven at 50 ℃ for 24 hours to finally obtain the polybutadiene polymer dispersed with silicon dioxide. The sample is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm, a tensile test is carried out by a tensile testing machine, the tensile rate is 50mm/min, the tensile strength of the sample is 2.16 +/-0.88 MPa, the tensile modulus is 3.85 +/-1.27 MPa, and the elongation at break is 562 +/-148%. And (3) recovering the stretch-broken polymer sample, applying a certain pressure, placing in a vacuum oven at 80 ℃, heating and placing for 4-6h, wherein the section can be automatically bonded, and reshaping. In this embodiment, the polymer sample can be used as a sealing plug or sealant by utilizing the functional characteristics of the polymer sample.

Example 18

Weighing 20g of phenylboronic acid modified silicone rubber (a) (prepared by taking methyl vinyl silicone rubber and 4-mercaptophenylboronic acid as raw materials and DMPA as a photoinitiator through mercaptan-olefin click addition reaction under the ultraviolet irradiation condition), 20g of silanol modified silicone rubber (b) (prepared by taking methyl vinyl silicone rubber and gamma-mercaptopropyl methyldimethoxysilane as raw materials and DMPA as a photoinitiator through mercaptan-olefin click addition reaction under the ultraviolet irradiation condition to obtain an intermediate product, hydrolyzing the intermediate product to obtain a final product), 12g of maleimide modified silicone rubber (c) (prepared by taking mercapto modified silicone rubber as a raw material and utilizing maleimide modification), 10g of white carbon black, 10g of titanium dioxide, 1.7g of ferric oxide and 0.05g of silicone oil are added into a small internal mixer to be mixed for 30min so that the additive and the sizing material are fully and uniformly mixed, taking out the rubber material, and carrying out heat treatment for 1h at the temperature of 120 ℃. And taking out the rubber material, placing the rubber material in a proper mould, placing the mould in a vacuum oven at 80 ℃ for 4h, and then forming the mould under the pressure of 10MPa to obtain the silicon rubber-based dynamic polymer material. A dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm is manufactured by a mould, a tensile test is carried out by a tensile testing machine, the tensile rate is 50mm/min, the tensile strength of the sample is 3.14 +/-0.97 MPa, the tensile modulus is 7.35 +/-1.64 MPa, and the breaking elongation is 1892 +/-254%. The polymer material has certain strength and surface elasticity, and a certain tensile force can be applied to the polymer material to stretch the polymer material in a larger range. The obtained polymer material can be made into a sealing ring, a cable insulating layer or an encapsulating material.

Example 19

The macromolecular compound (III) is used for preparing dynamic polymers with a single hybrid cross-linked network.

adding 120ml of chloroform solvent into a dry clean reaction bottle, introducing nitrogen to remove water and remove oxygen for 1h, then adding 25g of modified polycarbonate compound (a) (extracting limonene oxide from orange peel, carrying out polymerization reaction on the limonene oxide and carbon dioxide under the catalysis of β -diimine zinc to obtain polycarbonate PLimC, then carrying out click reaction on the polycarbonate PLimC and [4- (mercaptomethyl) phenyl ] neopentyl glycol borate, gamma-mercaptopropylmethyldimethoxysilane and N- [ (2-mercaptoethyl) carbamoyl ] propionamide by thiol-ene), heating to 60 ℃, stirring and dissolving, then dropwise adding a small amount of 20% acetic acid aqueous solution, stirring and mixing for 30min, then adding 2ml of triethylamine, reacting for 3h under the protection of nitrogen, then placing the reaction solution into a suitable mold, drying for 24h in a vacuum oven at 50 ℃, finally obtaining a transparent polymer block sample, preparing the transparent polymer block sample into a dumbbell type sample with the size of 80.0 x 10.0 x (2.0-4.0) mm, carrying out a tensile test by using a tensile testing machine, placing the sample in an external tensile testing machine, placing the sample into a transparent sample with the tensile strength of 25.02 x (2.0 x 2.0-4.0), placing the sample into an external packaging box, and carrying out a transparent testing, and carrying out a transparent test, and placing the transparent test, wherein the tensile testing the sample with the tensile testing time, and the tensile strength of the sample, and the sample.

Example 20

Taking a certain amount of modified polynorbornene (a) (vinyl boric acid and cyclopentadiene are used as raw materials, preparing boric acid modified norbornene through Diels-Alder reaction, reacting vinylamine with ethoxycarbonyl isocyanate, then reacting with cyclopentadiene through Diels-Alder reaction to prepare amido modified norbornene, heating and dissolving boric acid modified norbornene, amido modified norbornene and norbornene in an o-dichlorobenzene solvent to prepare a 0.1mol/L solution, taking 50ml of the solution from the solution, adding a small amount of deionized water and acetic acid dropwise, and stirring uniformly for later use. 4.24g of silane compound (b) (prepared by thiol-ene click reaction using 1, 6-hexanedithiol and allyldimethylethoxysilane as raw materials) was slowly added to the polynorbornene solution while the solution was heated in a water bath at 80 ℃ and the mixture was uniformly mixed by stirring. After the solution is added, the solution is continuously stirred for 30min, then 4ml of triethylamine is added, and the reaction is continuously carried out for 4h at the temperature of 80 ℃ to obtain a dynamic polymer solution. By utilizing an electrostatic spinning technology, a needle tube filled with a dynamic polymer solution is used as a positive electrode, a round aluminum plate is used as a negative electrode, the distance between electric fields is adjusted, voltage is applied, liquid drops of a needle head are changed into a spindle shape from a spherical shape through adjustment, a jet flow is formed, a solvent is partially volatilized in the spinning process, polymer fibers are obtained on a receiving screen, and then the fibers are placed in a vacuum oven at 60 ℃ to be dried for 12 hours, so that a dynamic polymer fiber product is obtained. The fiber diameter is observed by a microscope, and the diameter of the obtained polymer fiber is found to be in the range of 1-2 mu m. The prepared polynorbornene fiber can be used for manufacturing human organs, electronic packaging materials or corrosion-resistant materials of silicon integrated circuits, and has huge application prospects in the aspects of nano-tubes, optical fibers and integrated circuits.

Example 21

Weighing 22g of phenylboronic acid graft modified butyl rubber (a) (prepared by mercaptan-olefin click addition reaction under the ultraviolet irradiation condition by using brominated butyl rubber and 4-mercaptophenylboronic acid as raw materials and DMPA as a photoinitiator), 23g of silane graft modified butyl rubber (b) (prepared by mercaptan-olefin click addition reaction under the ultraviolet irradiation condition by using brominated butyl rubber and mercaptomethyldiethoxysilane as raw materials and DMPA as a photoinitiator), 25g of modified butyl rubber (c) (prepared by mercaptan-2-mercaptoethyl) carbamoyl ] propionamide as raw materials and DMPA as a photoinitiator, and by mercaptan-olefin click addition reaction under the ultraviolet irradiation condition), mixing uniformly, adding into a small internal mixer, mixing for 20min, adding 5g of white carbon black, 6g of titanium dioxide, 0.05g of barium stearate and 0.15g of stearic acid, and continuously mixing for 20 min. Taking out the mixed materials, cooling, placing the materials in a double-roller machine to be pressed into sheets, cooling at room temperature, cutting the sheets, taking out the prepared polymer sheets, soaking the polymer sheets in a water bath at 90 ℃ for crosslinking, then placing the polymer sheets in a vacuum oven at 80 ℃ for 5 hours for further reaction and drying, and finally obtaining the rubbery dynamic polymer material which has good plasticity, can be prepared into products with different shapes according to the size of a mould, can be stretched and extended within a certain range, and shows good tensile toughness. The sample is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm, and a tensile test is carried out by a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 1.72 +/-0.67 MPa, the tensile modulus is 3.52 +/-1.01 MPa, and the elongation at break is 1578 +/-262%. After the surface of the polymer sample is scratched by a blade and placed in a vacuum oven at 60 ℃ for 4-5 hours, the scratch disappears (the surface can be selected to be slightly wetted in the process), and the self-repairing effect is realized. The polymer material can generate creep deformation under the action of external force, can be stretched in a large range, and can be made into a magic plasticine toy with super toughness.

Example 22

Weighing 12g of borate modified polystyrene (a) (prepared by taking AIBN as an initiator and styrene and 4-vinylbenzeneboronic acid propylene glycol ester through free radical copolymerization), 13g of silane modified polystyrene (b) (prepared by taking AIBN as an initiator and utilizing styrene and styrene ethyl trimethoxy silane through free radical copolymerization), 15g of modified polystyrene (c) (prepared by taking 2-aminoethyl acrylate and 4-biphenylcarbonyl chloride as an initiator to obtain an acrylate monomer containing amido bonds under the catalysis of triethylamine, then taking AIBN as an initiator and performing free radical copolymerization with styrene) into a dry clean beaker, pouring 120ml of toluene solvent into the beaker, heating the beaker to 60 ℃, dissolving the mixture through stirring, adding a small amount of 20% acetic acid aqueous solution, continuing to react for 4 hours, then placing the mixed solution into a proper mold, drying for 24 hours in a vacuum oven at 60 ℃, finally, the hard massive polymer solid is obtained, and has higher surface hardness, certain mechanical strength and poorer elasticity and toughness. Crushing a polymer sample by using a hammer, placing the crushed polymer sample into a mold, heating the crushed polymer sample to 180 ℃, carrying out compression molding for 5min under the pressure of 5MPa, preparing the crushed polymer sample into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0), carrying out a tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, the measured tensile strength of the sample is 7.94 +/-2.35 MPa, the tensile modulus is 17.42 +/-3.17 MPa, the sample has good chemical resistance, and the prepared polymer material can be used as a substitute of a glass product and a hard packaging box.

Example 23

Weighing 30g of phenylboronic acid modified styrene-maleic anhydride copolymer (a) (prepared by reacting 4-aminobenzeneboronic acid with styrene-maleic anhydride copolymer by using p-toluenesulfonic acid as a catalyst), 28g of silane modified styrene-maleic anhydride copolymer (b) (prepared by reacting 3-aminopropylmethyldimethoxysilane with styrene-maleic anhydride copolymer by using p-toluenesulfonic acid as a catalyst), 6.3g of 1- (6-aminohexyl) -3-ethylurea (c) (prepared by reacting hexamethylene diamine and ethyl isocyanate as raw materials), 0.18g of p-toluenesulfonic acid, 1.74g of di-n-butyltin dilaurate, 5.8g of dioctyl phthalate, 12g of foaming agent F141b, 0.24g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010, uniformly mixing, adding into a small internal mixer for banburying and blending, and the mixing temperature is controlled below 40 ℃. After mixing, taking out the sample, putting the sample into a compression mold, closing the mold, pressurizing and heating, wherein the mold pressing temperature is 100-110 ℃, the mold pressing time is 10-15min, and the pressure is 10MPa, then putting the demolded pre-foamed blank into hot water with the temperature of more than 95 ℃, boiling the pre-foamed blank for 4h, taking out the pre-foamed blank, placing the pre-foamed blank in a vacuum oven with the temperature of 80 ℃ for further reaction and drying to finally obtain a polystyrene-based foamed polymer sample, preparing the polystyrene-based foamed polymer sample into a block-shaped sample with the size of 20.0 multiplied by 20.0mm, and carrying out compression performance test by using a universal testing machine, wherein the compression rate is 2mm/min, and the measured compression strength of the sample is 0.48 +/-0. The obtained polymer foam material has light weight and good heat preservation and insulation effects, and can be widely applied as a packaging material for valuables, precise instruments, vegetables, fruits and aquatic products.

Example 24

Preparing a dynamic polymer with a single hybrid cross-linked network by using a macromolecular organic boron compound (I), a macromolecular silicon-containing compound (II), a macromolecular compound (V) and a small molecular compound (V).

20g of phenylboronate modified polybutadiene (a) (prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on 4-mercaptophenylboronic acid pinacol ester and terminal amino polybutadiene), 15g of silane modified polybutadiene (b) (prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on mercaptomethyldiethoxysilane and terminal amino polybutadiene), 5g of amide modified polybutadiene (c) (prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on N- [ (2-mercaptoethyl) carbamoyl ] propionamide and terminal amino polybutadiene) are heated to 80 ℃ and mixed uniformly, 1.0g of distilled water and 1.2g of triethylamine are added, after stirring and reacting for 4 hours, 0.2g of dibutyltin dilaurate and 0.8g of silicon oil foam stabilizer are added, stirring at high speed, mixing, adding 4.14g trimethyl-1, 6-hexamethylene diisocyanate (d), stirring at high speed for 30s, pouring into proper mould when the mixture turns white and foams, and molding and foaming at 80 deg.C for 12h to obtain the final product. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by a universal tester, the compression rate is 2mm/min, and the compression strength of the sample is measured to be 0.43 +/-0.11 MPa. The obtained polyurethane foam material has good heat insulation performance, has the advantages of small density, high specific strength, recyclability, self-repairing property and the like, and can be applied to the preparation of recyclable foam filling materials.

Example 25

Preparing a dynamic polymer with a single hybrid crosslinking network by using a small molecular organic boron compound (I) and a large molecular silicon-containing compound (II).

Adding 12.5g of organic boron compound (a) (prepared by taking 4-hydroxy benzene boronic acid pinacol ester and 1, 6-hexamethylene diisocyanate as raw materials to react) into a dry and clean reaction bottle, adding 200ml of THF solvent, heating to 60 ℃, stirring and dissolving, then dropwise adding a small amount of 20% acetic acid aqueous solution, heating to 60 ℃, slowly adding 38g of silane modified polypropylene oxide copolymer (b) (epoxy compound 1 is prepared by using ethylene oxide-2-carbamate to react with ethyl isocyanate, propylene glycol, propylene oxide and epoxy compound 1 are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, synthesizing propylene oxide copolymer with a urea bond at a side group through cationic ring-opening polymerization, and then reacting the propylene oxide copolymer with 3-aminopropyltrimethoxysilane and 1, 6-hexamethylene diisocyanate to obtain a final product), after stirring and mixing for 30min, 2ml of triethylamine is added, and stirring and reaction are continued for 4h under the protection of nitrogen at 80 ℃. Then cooling to 60 ℃, adding 3.8g of microsphere foaming agent, 0.28g of stannous octoate, 2g of expanded graphite and 2g of ammonium polyphosphate, quickly stirring for 30s, uniformly mixing, continuously stirring and reacting for 2h in a nitrogen atmosphere to obtain a cross-linked network, pouring reactants into a proper mould, placing the mould in a vacuum oven at 60 ℃ for continuous reaction for 12h, cooling to room temperature, placing for 30min, and carrying out foam molding by using a flat vulcanizing machine, wherein the mould pressing temperature is 140-150 ℃, the mould pressing time is 10-15min, and the pressure is 10MPa, finally obtaining the soft polyurethane foam material with the flame retardant effect, pressing the surface of the sample by using fingers, and the sample can rebound, and in addition, the sample can also be expanded within a certain range. In the embodiment, the polymer material can be applied to the fields of sofa furniture, pillows, cushions, clothes, sound-insulating linings and the like, and plays roles in flame retardance and buffering.

Example 26

Weighing 25g of boric acid graft modified polypropylene (a) (using dicumyl peroxide as an initiator and maleic anhydride for graft modification of low molecular weight polypropylene; then using p-toluenesulfonic acid as a catalyst and 1-aminoethylboric acid for graft reaction with maleic anhydride for graft reaction of polypropylene to obtain a final product), 26g of silane graft modified polypropylene (a) (using dicumyl peroxide as an initiator and maleic anhydride for graft modification of low molecular weight polypropylene; then using p-toluenesulfonic acid as a catalyst and 3-aminopropylmethyldimethoxysilane for graft reaction with maleic anhydride for graft reaction of polypropylene to obtain a final product), 20mg of BHT antioxidant, adding the BHT antioxidant into a dry clean three-neck flask, heating to 160 ℃ under the protection of nitrogen, stirring and melting, then dropwise adding a small amount of 20% acetic acid aqueous solution, continuing the reaction for 3 hours, and when the melt has higher viscosity, 2.90g of phenylglycine amide (c), 0.12g of p-toluenesulfonic acid, 1.0g of plasticizer DOP and 0.25g of simethicone are added, and the reaction is continued for 2h under the protection of nitrogen. And then placing the sample into a proper mould, carrying out compression molding at 120 ℃ by using a molding press, placing the molded sample into a vacuum oven at 80 ℃ for continuous reaction for 4-6h, cooling to room temperature, and placing for 30min to finally obtain a blocky polypropylene-based polymer sample. The polymer sample has glossy surface, low hardness, certain strength and compressibility and can be stretched in a large range. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile testing machine at a tensile rate of 50mm/min, whereby the tensile strength of the specimen was 6.01. + -. 1.24MPa, the tensile modulus was 14.32. + -. 2.74MPa, and the elongation at break was 943. + -. 168%. The sample after the stretch breaking is stressed at the section (the section can be selected to be slightly wetted in the process), and the section can be bonded again after being placed in a mold at 100 ℃ for 6-8h, so that the sample has recyclability, and the material can be reshaped according to the mold with different shapes. The polymer material in the embodiment can be used as a polypropylene energy-absorbing buffer sheet with self-repairing property, can play a role in effectively dispersing impact force under the impact of external force, and can be repaired by heating when cracks or damages appear on the surface of the polymer material.

Example 27

Taking 40g of a phenylboronate ester graft modified ethylene-vinyl acetate copolymer (a) (prepared by taking an ethylene-vinyl alcohol-vinyl acetate copolymer as a raw material and reacting the phenylboronate ester graft modified ethylene-vinyl acetate copolymer with acryloyl chloride to obtain a copolymer with a double bond on a side chain, then reacting the copolymer with 2-mercaptophenylboronic acid pinacol ester through a thiol-ene click reaction to obtain a final product), 38g of a silane graft modified ethylene-vinyl acetate copolymer (b) (prepared by taking an ethylene-vinyl alcohol-vinyl acetate copolymer as a raw material and reacting the ethylene-vinyl acetate copolymer with acryloyl chloride to obtain a copolymer with a double bond on a side chain, and then reacting the copolymer with mercaptomethyl diethoxysilane through a thiol-ene click reaction to obtain a final product), 22g of a graft modified ethylene-vinyl acetate copolymer (c) (prepared by taking an ethylene-vinyl alcohol-vinyl acetate copolymer as a raw material and reacting the ethylene ether carbonyl isocyanate), Uniformly mixing 10g of AC foaming agent, 3g of zinc oxide, 10g of calcium carbonate, 0.4g of stearic acid, 0.1g of antioxidant 168, 0.2g of antioxidant 1010 and 0.4g of di-n-butyltin dilaurate, adding the mixture into a small internal mixer for banburying and blending, wherein the blending temperature is 100 ℃, the blending time is 10min, taking out a sample after the mixing is finished, putting the sample into a double-roller machine for pressing to prepare a sheet, cooling at room temperature, soaking the prepared polymer sheet into 90 ℃ water for pre-crosslinking, taking out, placing the sheet in a 80 ℃ vacuum oven for 6h for further reaction and drying, cooling to room temperature, and placing for 30 min. And taking the mixed sample sheet out of the mold, shearing the mixed sample sheet, placing a proper amount of the mixed sample sheet into a proper mold, 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 soft 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 having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile tester at a tensile rate of 50mm/min, whereby the tensile strength of the specimen was 3.47. + -. 0.88MPa, the tensile modulus was 5.12. + -. 1.45MPa, and the elongation at break was 822. + -. 173%. After the polymer material is cut off, the polymer material is placed in a mold at 120 ℃ and pressure is applied to the polymer material, so that the polymer material can be reshaped and can be reused by utilizing the self-repairing characteristic of the polymer material. In the present embodiment, the characteristics of light weight, good flexibility and toughness and self-repairing property of the obtained material are utilized, and the obtained material can be used for manufacturing a recyclable foam packaging material.

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

Claims

1. A dynamic polymer having a hybrid cross-linked network comprising dynamic covalent cross-links and supramolecular hydrogen-bonding cross-links; wherein said dynamic covalent crosslinks are effected by organoborate silicone linkages and said dynamic covalent crosslinks reach above the gel point of the dynamic covalent crosslinks in at least one crosslinking network; the supermolecule hydrogen bond crosslinking is formed by polymer chain side groups, side chains or side hydrogen bond groups on the side chains and the side chains;

wherein, the organic boric acid silicon ester bond has the following structure:

wherein at least one borosilicate silicone bond is formed between the boron atom and the silicon atom, at least one carbon atom in the structure is connected with the boron atom through the borosilicate bond, and at least one organic group is connected to the boron atom through the borosilicate bond;

wherein, the side hydrogen bond group comprises the following structural components:

2. the dynamic polymer with hybrid cross-linked network according to claim 1, characterized in that it further contains backbone hydrogen bonding groups; wherein, the skeleton hydrogen bond group comprises the following structural components:

3. the dynamic polymer with hybrid cross-linked network as claimed in claim 1, wherein the dynamic polymer contains only one cross-linked network, and the cross-linked network contains both organoborate silicate bond cross-links and supramolecular hydrogen bond cross-links, wherein the cross-linking degree of organoborate silicate bond cross-links is above the gel point.

4. The dynamic polymer with hybrid cross-linked network as claimed in claim 1, wherein the dynamic polymer contains two cross-linked networks, one of which contains only organoborate silicate ester linkage cross-links and the cross-linking degree of organoborate silicate linkage cross-links reaches above the gel point, and the other contains only supramolecular hydrogen bond cross-links.

5. The dynamic polymer with hybrid cross-linked network as claimed in claim 1, wherein the dynamic polymer contains two cross-linked networks, one of which contains both organoborate silicone bond cross-links and supramolecular hydrogen bond cross-links, and the cross-linking degree of organoborate silicone bond cross-links reaches above the gel point, and the other contains only organoborate silicone bond cross-links and the cross-linking degree of organoborate silicone bond cross-links reaches above the gel point.

6. The dynamic polymer with hybrid cross-linked network according to claim 1, characterized in that it is obtained by means of at least the following compound:

an organoboron compound (I) containing an organoboronic acid group, or an organoboronate group, or a combination of an organoboronic acid group and an organoboronate group; a silicon-containing compound (II) containing a silicon hydroxyl group, or a silicon hydroxyl group precursor, or a combination of a silicon hydroxyl group and a silicon hydroxyl group precursor; a compound (III) containing both an organoboronic acid group, or an organoborate group, or a combination of an organoboronic acid group and an organoborate group, and a silicon hydroxyl group, or a silicon hydroxyl group precursor, or a combination of a silicon hydroxyl group and a silicon hydroxyl group precursor; a compound (IV) containing organoborate silicone linkages and other reactive groups; a compound (V) which is free of organoboronate, silylhydroxy precursor, and organoboronate silyllinkage but contains other reactive groups; wherein the organoboron compound (I), the silicon-containing compound (II) and the compound (V) are not separately used as raw materials for preparing the dynamic polymer;

wherein, the organic boric acid group refers to a structural element composed of a boron atom and a hydroxyl group connected with the boron atom, the boron atom is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

wherein, the organoborate group refers to a structural unit composed of a boron atom, an oxygen atom linked to the boron atom, and a hydrocarbyl or silyl group linked to the oxygen atom, and wherein the boron atom is linked to at least one carbon atom through a boron-carbon bond, and at least one organic group is linked to the boron atom through the boron-carbon bond;

wherein, the silicon hydroxyl refers to a structural unit consisting of a silicon atom and a hydroxyl connected with the silicon atom;

wherein, the silicon hydroxyl precursor refers to a structural element consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom, wherein the group which can be hydrolyzed to obtain the hydroxyl group is selected from halogen, a cyano group, an oxygen cyano group, a sulfur cyano group, an alkoxy group, an amino group, a sulfate group, a borate group, an acyl group, an acyloxy group, an acylamino group, a ketoxime group and an alkoxide group;

wherein the other reactive group is selected from the group consisting of hydroxyl, carboxyl, carbonyl, acyl, amide, acyloxy, amino, aldehyde, sulfonic, sulfonyl, thiol, alkenyl, alkynyl, cyano, oxazinyl, oxime, hydrazino, guanidino, halogen, isocyanate, anhydride, epoxy, acrylate, acrylamide, maleimide, succinimide, norbornene, azo, azide, heterocyclic, triazolinedione, carbon radical, and oxygen radical.

7. The dynamic polymer having a hybrid cross-linked network as claimed in claim 6, wherein the organoboron compound (I) is represented by the following structure:

wherein A is a module containing an organic boric acid group, an organic borate group and an organic borate group; m is the number of the modules A, and m is more than or equal to 1; l is a substituent group on a single module A, or a connecting group between two or more modules A, and is selected from any one or more of the following structures: a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da, a polymer chain residue having a molecular weight of greater than 1000Da, a single bond, a heteroatom linking group, a divalent or multivalent small molecule hydrocarbyl 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; wherein, when m is 1, L is a substituent group on a single module A, and is selected from at least one of a small molecular hydrocarbon group with the molecular weight not more than 1000Da and a polymer chain residue with the molecular weight more than 1000 Da; when m >1, L is a linking group between two or more modules A, selected from at least one of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group having a molecular weight of not more than 1000Da, a divalent or polyvalent polymer chain residue having a molecular weight of more than 1000 Da; p is the number of groups L, and p is more than or equal to 1;

the silicon-containing compound (II) is represented by the following structure:

wherein G is a module containing a silicon hydroxyl group, or a silicon hydroxyl group precursor, or a silicon hydroxyl group and a silicon hydroxyl group precursor; n is the number of the modules G, and n is more than or equal to 1; j is a substituent group on a single module G, or a connecting group between two or more modules G, and is selected from any one or more of the following structures: hydrogen atoms, heteroatom groups, small molecular hydrocarbon groups with molecular weight not more than 1000Da, polymer chain residues with molecular weight more than 1000Da, inorganic small molecular chain residues with molecular weight not more than 1000Da, inorganic large molecular chain residues with molecular weight more than 1000Da, single bonds, heteroatom connecting groups, divalent or multivalent small molecular hydrocarbon groups with molecular weight not more than 1000Da, divalent or multivalent polymer chain residues with molecular weight more than 1000Da, divalent or multivalent inorganic small molecular chain residues with molecular weight not more than 1000Da, and divalent or multivalent inorganic large molecular chain residues with molecular weight more than 1000 Da; when n is 1, J is a substituent group on a single module G and is selected from at least one of a hydrogen atom, a heteroatom group, a small molecular hydrocarbon group with the molecular weight not more than 1000Da, a polymer chain residue with the molecular weight more than 1000Da, an inorganic small molecular chain residue with the molecular weight not more than 1000Da and an inorganic large molecular chain residue with the molecular weight more than 1000 Da; when n >1, J is a linking group between two or more modules G, selected from at least one of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group with a molecular weight of not more than 1000Da, a divalent or polyvalent polymer chain residue with a molecular weight of more than 1000Da, a divalent or polyvalent inorganic small molecule chain residue with a molecular weight of not more than 1000Da, and a divalent or polyvalent inorganic large molecule chain residue with a molecular weight of more than 1000 Da; q is the number of groups J, and q is more than or equal to 1;

the compound (III) represented by the following structure:

wherein A is a module containing an organic boric acid group, an organic borate group and an organic borate group; x is the number of the modules A, and x is more than or equal to 1; g is a module containing a silicon hydroxyl group, a silicon hydroxyl group precursor, or a silicon hydroxyl group and a silicon hydroxyl group precursor; y is the number of the modules G, and y is more than or equal to 1; t is a connecting group between two or more A, two or more G, or A and G, and is selected from any one or any several structures of the following: single bonds, heteroatom linkers, divalent or multivalent small molecule hydrocarbyl groups having a molecular weight of no more than 1000Da, and divalent or multivalent polymer chain residues having a molecular weight greater than 1000 Da; v is the number of groups T, and v is more than or equal to 1;

the compound (IV) represented by the following structure:

wherein E is a module containing an organoborate silicone bond; u is the number of the modules E, and u is more than or equal to 1; y is a substituent group on a single module E, or a substituent group on a single module E and a linking group between two or more modules E, and at least one group Y is linked to a boron atom of an organoboronate silicone bond and at least one group Y is linked to a silicon atom of an organoboronate silicone bond; wherein at least one group Y contains at least one other reactive group, and the number of other reactive groups contained in all groups Y is 2 or more; the group Y is selected from any one or any several structures of the following structures: a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da, a polymer chain residue having a molecular weight of greater than 1000Da, a single bond, a heteroatom linking group, a divalent or multivalent small molecule hydrocarbyl 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; wherein, when u is 1, Y is a substituent group on a single module E, and is selected from at least one of small molecular hydrocarbon groups with the molecular weight not more than 1000Da and polymer chain residues with the molecular weight more than 1000 Da; u >1, Y is a substituent group on a single module E and a linking group between two or more modules E selected from at least one of a small molecule hydrocarbyl group having a molecular weight of no more than 1000Da, a polymer chain residue having a molecular weight of greater than 1000Da, and at least one of a single bond, a heteroatom linking group, a divalent or multivalent small molecule hydrocarbyl 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; r is the number of the groups Y, and r is more than or equal to 2;

wherein, the module A containing organic boric acid group is selected from any one or several structures of the following:

wherein, K₁Is a group directly attached to the boron atom and selected from any 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; wherein, the cyclic structure in A4 is a non-aromatic or aromatic boron heterocyclic group containing at least one organic boric acid group; the ring-forming atoms of the cyclic structure in A4 are each independently a carbon atom, a boron atom or other hetero atom, 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 bonded to the group L or the group T; 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 to the boron atoms through the boron-carbon bond;

the organic borate ester group-containing module A is selected from any one or any several structures of the following:

wherein, K₂Is a group directly attached to the boron atom and selected from any 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; r₁、R₂、R₃、R₄、R₆Is a monovalent organic group or a monovalent organosilicon group directly bonded to an oxygen atom through a carbon atom or a silicon atom, selected from any of the following structures: 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 greater than 1000 Da; r₅Is a divalent organic or divalent organosilicon group directly attached to two oxygen atoms, directly attached to the oxygen atoms through a carbon or silicon atom, selected from any of the following structures: a divalent small molecule hydrocarbon group having a molecular weight of no more than 1000Da, a divalent small molecule silane group having a molecular weight of no more than 1000Da, and a divalent polymer chain residue having a molecular weight greater than 1000 Da; wherein the cyclic structure in B5 is a non-aromatic or aromatic boracic group containing at least one organoboronate group; the ring-forming atoms of the cyclic structure in B5 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 organoborate group, and at least one ring-forming atom is linked to the group L or the group T; 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 to the boron atoms through the boron-carbon bond;

the module G containing the silicon hydroxyl is selected from any one or any several structures of the following:

wherein, K₃、K₄、K₅、K₆、K₇Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbyl with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da, and inorganic macromolecular chain residues with the molecular weight more than 1000 Da; wherein, the cyclic structure in C7, C8 and C9 is a nonaromatic or aromatic silacyclic group containing at least one silicon hydroxyl group; the ring-forming atoms of the cyclic structure in C7, C8, C9 are each independently a carbon atom, a silicon atom, or other hetero atom, 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 bonded to the group J or the group T;

the module G containing the silicon hydroxyl precursor is selected from any one or any several structures of the following:

wherein, K₈、K₉、K₁₀、K₁₁、K₁₂Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbyl with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da, and inorganic macromolecular chain residues with the molecular weight more than 1000 Da; x₁、X₂、X₃、X₄、X₅、X₆、X₇、X₈、X₉、X₁₀、X₁₁、X₁₂、X₁₃、X₁₄Is a hydrolyzable group directly bonded to the silicon atom selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide; wherein, the cyclic structure in D7, D8 and D9 is a nonaromatic or aromatic silacyclic group containing at least one silicon hydroxyl precursor; the ring-forming atoms of the cyclic structure in D7, D8, D9 are each independently a carbon atom, a silicon atom or another hetero atom, andat least one ring-forming atom is a silicon atom and constitutes a silicon hydroxyl precursor, and at least one ring-forming atom is linked to the group J or the group T;

the module E containing the organic borate silicon ester bond is selected from any one or any several structures of the following:

wherein, K₁₃、K₁₆、K₂₀Are groups directly attached to the boron atom, each independently selected from any 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; k₁₄、K₁₅、K₁₇、K₁₈、K₁₉、K₂₁Are groups directly attached to the silicon atom, each independently selected from any of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups with the molecular weight not more than 1000Da, polymer chain residues with the molecular weight more than 1000Da, inorganic micromolecular chain residues with the molecular weight not more than 1000Da and inorganic macromolecular chain residues with the molecular weight more than 1000 Da.

8. The dynamic polymer with hybrid cross-linked network as claimed in claim 7, wherein the heteroatom group is selected from any one of the following groups: halogen, hydroxyl, thiol, carboxyl, nitro, primary amino, silicon, phosphorus, triazole, isoxazole, amide, imide, thioamide, enamine, carbonate, thiocarbonate, dithiocarbonate, trithiocarbonate, carbamate, thiocarbamate, dithiocarbamate, thioester, dithioester, orthoester, phosphate, phosphite, phosphinate, phosphonate, phosphoryl, phosphoramidite, hypophosphoryl, thiophosphoryl, thiophosphorous acyl, phosphosilane, silane, carboxamide, thioamide, phosphoramidite, pyrophosphoro, cyclophosphamide, ifosfamide, thiophosphoryl, orthosilicic acid, metasilicic acid, silicic acid, boric acid, metaboric acid, boric acid, sodium, potassium, magnesium, aconitoyl, peptide bond, acetal, cyclic acetal, mercaptal, azaacetal, azathioacetal, azathioketal, dithioacetal, hemiacetal, thiohemiacetal, azahemiacetal, ketal, thioketal, azaketal, azathioketal, thioketal, acylhydrazone bond, oxime bond, thiooxime ether group, semicarbazone bond, thiosemicarbazone bond, hydrazine group, hydrazide group, thiocarbohydrazide group, azocarbohydrazide group, thioazohydrazide group, hydrazonoformate group, hydrazonothiocarbamate group, carbazepine group, thiocarbhydrazide, azo group, isourea group, isothiourea group, allophanate group, thioallophanate group, guanidino group, amidino group, aminoguanidino group, imido group, thioester group, nitroxyl group, nitrosyl group, sulfonic acid ester group, sulfinic acid ester group, sulfonamide group, sulfenamide group, sulfonylhydrazide group, hydrazono group, thiosemicarbazide group, guanidyl group, aminoguanidino group, thiosemicarbaz, Sulfonylurea groups, maleimides, triazolinediones;

the small molecule alkyl with the molecular weight not more than 1000Da is selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and the combination thereof: c_1-71Alkyl, ring C_3-71Alkyl, phenyl, benzyl, aryl;

the polymer chain residue with the molecular weight of more than 1000Da is selected from carbon chain polymer residue, heterochain polymer residue and element organic polymer residue in a homopolymerization or copolymerization mode;

the small molecule silane group with the molecular weight not more than 1000Da is selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and combination thereof: a silicone chain residue, a siloxane chain residue, a thiosiloxane chain residue, a silazane chain residue;

the inorganic small molecular chain residue with the molecular weight not more than 1000Da is selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and combination thereof: chain sulfur residue, silane chain residue, silicon oxide chain residue, sulfur nitrogen compound chain residue, phosphazene compound chain residue, phosphorus oxide chain residue, borane chain residue, boron oxide chain residue;

the inorganic macromolecular chain residue with the molecular weight of more than 1000Da is selected from any one of the following groups, any unsaturated form, any substituted form, any hybridized form and combination thereof: chain sulfur polymer residues, polysiloxane chain residues, polysulfide silicon chain residues, polysulfide nitrogen chain residues, polyphosphate chain residues, polyphosphazene chain residues, polychlorophosphazene chain residues, polyborane chain residues, polyboroxine chain residues; or any inorganic macromolecule with residues and residues, which is selected from the following groups, and is subjected to surface modification: zeolite-type molecular sieves, aluminum phosphate molecular sieves, zirconium phosphate molecular sieves, heteropolyacid salt molecular sieves, diamond, graphite, graphene oxide, carbon nanotubes, fullerene, carbon fiber, white phosphorus, red phosphorus, phosphorus pentoxide, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talc, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, sulfur nitride, calcium silicide, silicates, glass fiber, beryllium oxide, magnesium oxide, mercury oxide, borohydride, boron nitride, boron carbide, aluminum nitride, diaspore, gibbsite, corundum, titanium dioxide;

the single bond is selected from a boron-boron single bond, a carbon-carbon single bond, a carbon-nitrogen single bond, a nitrogen-nitrogen single bond, a boron-carbon single bond, a boron-nitrogen single bond, a borosilicate single bond, a silicon-silicon single bond, a silicon-carbon single bond and a silicon-nitrogen single bond;

the heteroatom connecting group is selected from any one or combination of the following groups: an ether group, a sulfur group, a disulfide group, a sulfide group, a divalent tertiary amine group, a trivalent tertiary amine group, a divalent silicon group, a trivalent silicon group, a tetravalent silicon group, a divalent phosphorus group, a trivalent phosphorus group, a divalent boron group, and a trivalent boron group.

9. The dynamic polymer with hybrid cross-linked network as claimed in claim 6, wherein the formulation components constituting the dynamic polymer further comprise any one or more of the following additives: other polymers, auxiliaries, fillers;

wherein, other polymers which can be added are selected from any one or more of the following: natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers;

wherein, the additive can be selected from any one or more of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, foaming agents, dynamic modifiers, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners and leveling agents;

wherein, the filler which can be added is selected from any one or more of the following materials: inorganic non-metal filler, metal filler and organic filler.

10. The dynamic polymer with hybrid crosslinking network as claimed in claim 1, wherein the crosslinking network skeleton chain of the dynamic polymer is composed of at least one segment selected from acrylate polymers, acrylamide polymers, polyether polymers, polyester polymers, polyamide polymers, polyurethane polymers and polyolefin polymers.

11. The dynamic polymer with hybrid cross-linked network according to claim 1, characterized by any of the following properties: solutions, emulsions, creams, gels, ordinary solids, foams.

12. A dynamic polymer having a hybrid cross-linked network comprising dynamic covalent cross-links and supramolecular hydrogen-bonding cross-links; wherein said dynamic covalent crosslinks are effected by organoborate silicone linkages and said dynamic covalent crosslinks reach above the gel point of the dynamic covalent crosslinks in at least one crosslinking network; the supermolecule hydrogen bond crosslinking is formed by participation of a side hydrogen bond group and a skeleton hydrogen bond group;

wherein, the organic boric acid silicon ester bond has the following structure:

wherein, the side hydrogen bond group and the skeleton hydrogen bond group contain the following structural components:

13. dynamic polymer with hybrid cross-linked network according to any of claims 1 to 6, 10, 11, 12, characterized in that it is applied to the following articles: the shock absorber comprises a shock absorber, a buffer material, an anti-impact protective material, a motion protective product, a military police protective product, a self-repairable coating, a self-repairable plate, a self-repairable binder, a bulletproof glass interlayer adhesive, a tough material, a shape memory material, a sealing element and a toy.