CN108359100A

CN108359100A - A kind of dynamic covalent polymer and its application

Info

Publication number: CN108359100A
Application number: CN201710056037.XA
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Iron Cloth Mstar Technology Ltd
Priority date: 2017-01-25
Filing date: 2017-01-25
Publication date: 2018-08-03
Also published as: WO2018137504A1

Abstract

The invention discloses a kind of dynamic covalent polymer, it includes there is a dynamic covalently inorganic boric acid estersil key, and the connected linker of the silicon atom in inorganic boric acid estersil keys wherein different from least two contains the carbon atom on dynamic covalent polymer chain.The dynamic covalent polymer has strong dynamic reversibility and energy dissipation because containing inorganic boric acid estersil key, and the functional characteristics such as stimulating responsive, self-repairability are embodied, it has a wide range of applications in fields such as athletic protective, functional coating, biomimetic materials.

Description

Dynamic covalent polymer and application thereof

Technical Field

The invention relates to the field of intelligent polymers, in particular to a dynamic covalent polymer formed by dynamic covalent bonds and application thereof.

Background

Conventional polymers generally consist of common covalent bonds, which have high bond energy and thermal stability, and thus lack dynamic properties while having good stability and mechanical properties. Dynamic polymers are a novel class of polymer systems formed by dynamic chemical bonds. The dynamic polymers can be classified into physical type dynamic polymers based on supramolecular forces and covalent type dynamic polymers based on dynamic covalent bonds, according to the difference of dynamic chemical bonds in the dynamic polymers. The covalent dynamic polymer constructed by the dynamic reversible covalent bond also has remarkable characteristics due to the special properties of the dynamic reversible covalent bond.

The dynamic covalent bond is a chemical bond which can generate controllable reversible reaction under a certain condition, is a relatively weaker covalent bond than a non-covalent bond, and can realize dynamic fracture and formation of the covalent bond by changing the external condition or spontaneously. The introduction of dynamic covalent bonds into polymers is a viable method for forming novel dynamic polymers. However, the conventional dynamic covalent bonds such as diels-alder reaction products, nitrogen oxides, etc. are often cleaved at high temperatures and the side reactions are severe. How to obtain a system with strong and controllable dynamic performance and wide application range is still a difficult problem in the prior art.

Disclosure of Invention

Against the background described above, the present invention provides a dynamic covalent polymer which exhibits excellent dynamic reversibility and can exhibit functional characteristics such as stimulus responsiveness, plasticity, self-repairability, recyclability, reworkability, and the like.

The invention is realized by the following technical scheme:

a dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-atoms and wherein the linking group to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms comprises a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein the linking group to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein the linking group bonded to any different Si atom of at least two different B-O-Si dynamic covalent bonds is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein any divalent and higher than divalent linking group bonded to a Si atom in any different B-O-Si dynamic covalent bond is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

The linking group L may be a linking group having a carbon atom in a low molecular weight or high molecular weight skeleton, preferably a high molecular linking group having a molecular weight of more than 1000Da, and more preferably a high molecular linking group having a molecular weight of more than 1000Da and having a number of carbon atoms in a skeleton of not less than 20. The linker L may also contain optional heteroatoms and/or atoms of elements that may form an organic group of elements in the backbone. The linker L may have any suitable topology including, but not limited to, linear, cyclic (including, but not limited to, monocyclic, polycyclic, nested, bridged), branched (including, but not limited to, star, H, comb, dendritic, hyperbranched), two-dimensional and three-dimensional clusters, and any suitable combination of the above structures. The linking group L may be a homopolymer or a copolymer. The linking group L may have any one or more glass transition temperatures.

According to embodiments of the present invention, a dynamic covalent polymer may contain different linkers L; in addition to the linker L, it may also contain some other linker to link different Si atoms in different B-O-Si, preferably (poly) siloxanes; the other linking groups may also have any suitable topology.

The dynamic covalent polymer described in the present invention may optionally further comprise an inorganic borono-oxygen bond (B-O-B).

The dynamic covalent polymer or its composition according to the present invention optionally further comprises supramolecular hydrogen bonding, wherein supramolecular hydrogen bonding may be intra-chain/intra-molecular non-crosslinking (intra-chain looping) and/or inter-chain/inter-molecular crosslinking and/or inter-chain/inter-molecular non-crosslinking (polymerization).

In the embodiment of the present invention, the form of the dynamic covalent polymer or the composition thereof can be solution, emulsion, paste, common solid, elastomer, gel (including hydrogel, organic gel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel), foam, and the like.

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

The invention also provides an energy absorption method, which is characterized in that a dynamic covalent polymer is provided and used as an energy absorption material for absorbing energy, wherein the dynamic covalent polymer contains B-O-Si dynamic covalent bonds, any one B atom is connected with three-O-, and a linking group L is contained in a linking group connected with different Si atoms in at least two B-O-Si dynamic covalent bonds based on different B atoms, and the linking group L contains carbon atoms on the main chain skeleton of the dynamic covalent polymer.

In the embodiment of the invention, the dynamic covalent polymer has wide adjustable performance range and wide application prospect, and particularly can be applied to the manufacture of products such as shock absorbers, buffer materials, sound insulation materials, noise elimination materials, impact resistance protection materials, motion protection products, military police protection products, self-repairing coatings, self-repairing plates, self-repairing adhesives, bulletproof glass interlayer adhesives, toughness materials, shape memory materials, toys and the like.

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

(1) in the invention, at least part of the inorganic borate silicon ester bonds have carbon atoms on the connecting groups, namely at least part of the polymer chains are carbon-containing chains, so that the advantages of the carbon-containing chain polymer can be fully exerted, including but not limited to rich chemical structures, rich topological structures and rich performances, a specific dynamic covalent polymer can be created, and the invention has more freedom degrees than the prior art, more excellent performances and wider application than the prior material.

(2) According to the invention, an inorganic borosilicate silicon ester bond and a part of optional inorganic boro-oxo-boro bond are used as dynamic covalent bonds to construct a dynamic covalent polymer, and optionally contain hydrogen bond action, so that the dynamic covalent polymer with specific performances of rapid self-repairing, sensitive stress/strain response and the like is obtained by fully utilizing the dynamic properties of the inorganic borosilicate silicon ester bond and the supermolecule hydrogen bond. Compared with the supermolecular polymer, the dynamic covalent polymer has stronger dynamic bond energy and different stimulus responsiveness, and shows specificity. Because common covalent cross-linking does not exist in the dynamic covalent polymer, the material can be completely self-repaired, shaped, recycled and reprocessed.

(3) The dynamic covalent polymer has rich structure and various performances, and the dynamic covalent components and the supermolecular components contained in the dynamic covalent polymer have controllability. By adjusting the number of functional groups, the molecular structure and the molecular weight in the raw material compound and/or introducing a group with reactivity, a group for promoting the dynamic property, a group with functionality and/or adjusting the parameters of the raw material composition and the like into the raw material compound, the dynamic covalent polymers with different structures can be prepared, thereby enabling the dynamic covalent polymers to embody various performances and meeting the application requirements of different occasions.

(4) The dynamic reactivity of the dynamic reversible bond in the dynamic covalent polymer is strong, and the dynamic reaction condition is mild. Compared with other existing dynamic covalent systems, the preparation method disclosed by the invention fully utilizes the good thermal stability and high dynamic reversibility of the inorganic boric acid silicon ester bond, can realize the synthesis and dynamic reversibility of the dynamic covalent polymer under the conditions of no need of a catalyst, no need of high temperature, illumination or specific pH, improves the preparation efficiency, reduces the limitation of the use environment and expands the application range of the polymer. In addition, by selectively controlling other conditions (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.

(5) Dynamic covalent polymers may exhibit functional properties. By adjusting dynamic components in the dynamic covalent polymer, the polymer can show stimulus responsiveness and dilatancy, and the polymer can respond to external stimuli such as external force, temperature, pH, illumination and the like to change the self state. After the dynamic reversible inorganic boric acid silicon ester bond and the supermolecule hydrogen bond are broken, the bonding can be carried out again by changing the external conditions, so that the material has the functional characteristics of plasticity, self-repairability and the like, the service life of the carbon chain-containing polymer is prolonged, and the carbon chain-containing polymer can be applied to certain special fields.

Detailed Description

In one embodiment of the present invention, a dynamic covalent polymer is provided comprising a B-O-Si dynamic covalent bond, wherein any one B atom is bonded to three-O-, and wherein the linking group bonded to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms comprises a linking group L comprising a carbon atom in the backbone of the dynamic covalent polymer backbone.

In another embodiment of the present invention, there is provided a dynamic covalent polymer comprising a B-O-Si dynamic covalent bond wherein any one B atom is bonded to three-O-, and wherein the linking group bonded to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms is a linking group L comprising a carbon atom in the backbone of the dynamic covalent polymer backbone.

In another embodiment of the present invention, there is provided a dynamic covalent polymer comprising a B-O-Si dynamic covalent bond wherein any one B atom is bonded to three-O-, and wherein the linking group bonded to any different Si atom of at least two different B-O-Si dynamic covalent bonds is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

In another embodiment of the present invention, there is provided a dynamic covalent polymer comprising a B-O-Si dynamic covalent bond wherein any one B atom is bonded to three-O-, and wherein any divalent and higher divalent linking group bonded to a Si atom in any different B-O-Si dynamic covalent bond is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

The linking group L in the embodiments of the present invention may be a linking group having a carbon atom in a low molecular weight or high molecular weight skeleton, preferably a high molecular linking group having a molecular weight of more than 1000Da, and more preferably a high molecular linking group having a molecular weight of more than 1000Da and having a number of carbon atoms in a skeleton of not less than 20. The linker L also contains an optional heteroatom and/or an element atom that can form an elemental organic group in the backbone, wherein the optional heteroatom can be any suitable heteroatom including, but not limited to O, N, S; the optionally contained element atom may be any suitable element atom including, but not limited to, P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir. Preferably, the linking group L is directly linked to the Si atom of the B-O-Si bond through a carbon atom, which not only allows the dynamics of the B-O-Si bond to be obtained, but also maximizes the utilization of the properties of the linking group L containing carbon atoms. The linker L may have any suitable topology including, but not limited to, linear, cyclic (including, but not limited to, monocyclic, polycyclic, nested, bridged), branched (including, but not limited to, star, H, comb, dendritic, hyperbranched), two-dimensional and three-dimensional clusters, and any suitable combination of the above structures, even particles (including fibers and plate-like particles) with common covalent crosslinks. The linking group L may be a homopolymer or a copolymer. When the linking group L has a glass transition temperature, it may have any one or more glass transition temperatures; if the glass transition temperature is higher than room temperature, the dynamic covalent polymer can be endowed with better rigidity and modulus; if the temperature is lower than room temperature, the dynamic copolymer can be imparted with better flexibility, elongation and moldability. The linking group L is preferably a hydrocarbon group, a polyolefin group, a polyether group, a polyester group, a polyurethane group, a polyurea group, a polythioamine group, a polyacrylate group, a polyacrylamide group, a polycarbonate group, a polyethersulfone group, a polyarylsulfone group, a polyetheretherketone group, a polyimide group, a polyamide group, a polyamine group, a polyphenylene ether group, a polyphenylene sulfide group, a polyphenylene sulfone group, but the present invention is not limited thereto. According to embodiments of the present invention, a dynamic covalent polymer may contain different linkers L.

In the present invention, the higher the proportion of the linking group L, the more the properties of the linking group L, such as a wide range of selectable glass transition temperatures, mechanical properties, chemical properties, optical properties, printing properties, and the like, can be exhibited. Preferably, the proportion of the sum of carbon atoms and heteroatoms present in the dynamic covalent polymer skeleton in the linking group L relative to all atoms present in the dynamic covalent polymer skeleton is not less than 50 mol%, more preferably not less than 80 mol%. The higher the proportion of carbon and heteroatoms present, the more the properties of the carbon-containing linker L are exerted.

In the present invention, the linking group may be any other suitable linking group besides the linking group L, including but not limited to an element linking group, a hetero-element linking group; wherein an elemental linker means that the linker backbone consists of elemental atoms and a heteroelement linker means that the linker backbone consists of heteroatoms and elemental atoms. The other linking group is preferably a (poly) siloxane, including cross-linked silica, most preferably a polysiloxane; the other linking groups may also have any suitable topology and a dynamic covalent polymer may contain different other linking groups.

According to an embodiment of the present invention, the dynamic covalent polymer further optionally comprises an inorganic borono-oxygen bond (B-O-B).

The term "polymerization" reaction as used in the present invention is a process/action of chain extension, and includes a process in which a reactant synthesizes a product having a higher molecular weight by a reaction form of 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, and a crosslinking process of a reactant molecular chain.

The term "cross-linking" reaction as used in the present invention refers primarily to the process of chemical linking of supramolecules through chemical and/or hydrogen bonding of covalent bonds between and/or within reactant molecules to form products with two-dimensional, three-dimensional clusters and thus three-dimensional infinite network structures. 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 term "crosslinked" in the present invention refers specifically to a three-dimensional infinite network structure above the gel point (including the same below), and "uncrosslinked" includes structures below the gel point such as linear, branched, cyclic, two-dimensional cluster, and three-dimensional cluster structures below the gel point.

The "gel point" in the present invention means a reaction point at which the reactants undergo a sudden increase in viscosity during crosslinking and begin to undergo gelation and reach a three-dimensional infinite network for the first time, which is also referred to as a percolation threshold. A crosslinked product above the gel point having a three-dimensional infinite network structure, the crosslinked network forming an integral and spanning the entire polymer structure; the crosslinked product below the gel point is only a loose linked structure and does not form a three-dimensional infinite network structure, and only a small amount of the three-dimensional network structure exists locally, and does not belong to a crosslinked network which can form a whole body and spans the whole polymer structure.

The term "common covalent bond" as used herein refers to a covalent bond in the conventional sense other than dynamic covalent bond, which is difficult to break at 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.

The term "dynamic covalent bond" as used in the embodiments of the present invention refers to inorganic borosilicate silicon bonds (B-O-Si) and optionally inorganic boro-oxo-boron bonds (B-O-B). It is noted that in embodiments of the present invention, the inorganic boron-oxygen-boron bonds can be adjusted and controlled based on the choice of the reaction materials and the formulation ratio.

In the present invention, the dynamic covalent polymer comprises dynamic covalent polymer molecules that may have any suitable topology or topologies, including, but not limited to, linear, cyclic (including, but not limited to, monocyclic, polycyclic, nested, bridged), branched (including, but not limited to, star, H, comb, dendritic, hyperbranched), two-dimensional/three-dimensional clusters, three-dimensional infinite network cross-linked structures, and combinations thereof. The polymer chain can have a side group, a side chain and a branched chain, and the side group, the side chain and the branched chain can be continuously provided with the side group, the side chain and the branched chain, namely, the polymer chain can have a multistage structure.

In the present invention, the dynamic covalent polymer and the crosslinked network in the composition thereof are both dynamic covalent crosslinked networks, and once the dynamic covalent crosslinking is dissociated, the crosslinked structure is dissociated. But particles with common covalent cross-linking (including fibers and plate-like particles) in filled form are not excluded. The dynamic covalent crosslinking is also based on inorganic boric acid silicon ester bonds (B-O-Si) and optional inorganic boron oxygen boron bonds (B-O-B) to realize crosslinking. In embodiments of the invention, the dynamic covalent bond may also be present in non-crosslinked polymers/small molecules. Thus, the dynamic covalent polymer may be a dynamic covalently crosslinked polymer or a non-dynamic covalently crosslinked polymer.

In the present invention, the inorganic boro-oxy-boron bond is less dynamic than the inorganic boro-silicate bond. The dynamic covalent polymer with adjustable dynamics can be obtained by adjusting and controlling the quantity and the proportion of inorganic boron-oxygen-boron bonds.

In an embodiment of the present invention, the dynamic covalent bond may be present on both the side groups and/or side chains and/or branches and/or bifurcations of the main chain and the next and/or next multiple of the side groups and/or side chains and/or branches and/or bifurcations of the main chain, in addition to the backbone of the main polymer chain to form the dynamic covalent polymerization/crosslinking. The invention also does not exclude the inclusion of dynamic covalent bonds at the same time on the side groups and/or end groups of the polymer chains. Wherein only dynamic covalent bonds on the crosslinked network backbone can form dynamic covalent crosslinks. Dynamic covalent bonds at any position in the dynamic covalent polymer may participate in dynamic reversible exchange under appropriate conditions. In the crosslinked network structure of dynamic covalent polymers, once the dynamic covalent bonds that make up the dynamic covalent crosslinks dissociate, the overall effective degree of crosslinking of the polymer system will decrease. The number of inorganic borosilicate bonds in the backbone between any two of the nearest crosslinks containing inorganic borosilicate bonds (in proportion to all bonds) is not limited, and may be one or more, preferably contains only one. When only one is contained, the dynamic covalent polymer structure is more regular, and the dynamic property is more controllable.

The dynamic covalent polymers and compositions thereof described in the present invention optionally also include supramolecular hydrogen bonding, wherein supramolecular hydrogen bonding may be intra-chain/intramolecular non-crosslinking (intra-chain/intramolecular ring formation) and/or inter-chain/intermolecular crosslinking and/or inter-chain/intermolecular non-crosslinking (polymerization). In an embodiment of the invention said optionally contained supramolecular hydrogen bonding consists of hydrogen bonding between hydrogen bonding groups present at any one or more of the polymer backbone, side groups, side chains, branches, end groups of any suitable composition in the dynamic covalent polymer. Wherein said hydrogen bonding groups may also be present in the small molecule and/or the filler. In embodiments of the present invention, the hydrogen bonding groups are preferably present on the polymer chains containing the B-O-Si bonds, facilitating better synergy of dynamic covalent bonds and hydrogen bonds.

In embodiments of the invention, one or more polymers may be included in the dynamic covalent polymer composition; when a crosslinked network is present, it may be composed of one or more crosslinked networks, or may contain a non-crosslinked polymer component. When the dynamic covalent 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, or two or more crosslinked networks partially interpenetrating with each other, but the present invention is not limited thereto; wherein two or more crosslinked networks may be the same or different. When the dynamic covalent polymer comprises both crosslinking and non-crosslinking components, the non-crosslinking components may be homogeneously blended/interspersed within the crosslinked network, or may be non-homogeneously dispersed within the crosslinked network; the plurality of non-crosslinking ingredients may be homogeneously blended or incompatible.

With the dynamic covalent polymers of the invention, it is ensured that the polymer can have a crosslinked structure under specific conditions even in the case of only one crosslinked network, when the dynamic covalent crosslinks reach above the gel point of the dynamic covalent crosslinks in at least one crosslinked network.

In the present invention, the "backbone" refers to the chain length direction of the polymer; for crosslinked polymers, the term "backbone" refers to any segment present in a crosslinked network backbone, including the backbone and crosslinking linkages on an infinite three-dimensional network backbone; for non-crosslinked polymers, the "backbone" generally refers to the chain with the most mer, unless otherwise specified. Wherein, the side chain refers to a chain structure which is connected with the main chain skeleton of the polymer and is distributed beside the main chain skeleton; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is linked to the polymer chain skeleton and is distributed beside the chain skeleton. For "side chains", "branches" and "side groups", it may have a multi-stage structure, i.e. a side chain/branch may continue to carry side groups and side chains/branches, and a side chain/branch of a side chain/branch may continue to have side groups and side chains/branches. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. For hyperbranched and dendritic chains and their related branched chain structures, the branches may also be considered as main chains, but in the present invention, the outermost chains are considered as branches and the other chains as main chains.

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.

Based on the dynamics and responsiveness of the dynamic covalent bonds and optional hydrogen bonds, the dynamic covalent polymers of the present invention can exhibit a wide variety of dynamic properties and responsiveness to external stimuli, including, but not limited to, self-healing, temperature responsiveness, stress/strain responsiveness, and particularly dilatant properties. When the dynamic covalent polymer is in a non-crosslinked structure, the system will remain in a viscous state without producing an elastic state even if dilatant behavior occurs under stress/strain, which facilitates complete loss of mechanical energy through viscous flow. When the dynamic covalent polymer is in a dynamic cross-linked structure, when the system generates dilatant flow, the viscosity-elasticity conversion or elasticity enhancement occurs, and the viscosity loss to external force can be generated and the damage to the external force is reduced. Both cases have features and advantages. The self-repairing property and the temperature responsiveness related to the dynamic property are beneficial to self-repairing, shaping, recycling and the like of the dynamic covalent polymer, the use safety of the material is improved, the service life of the material is prolonged, the processability of the material is improved, and the like.

In an embodiment of the present invention, the inorganic borosilicate linkage (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxyl group and/or a silicon hydroxyl precursor.

The inorganic boron compound refers to a boron-containing compound in which a boron atom in the compound is not connected with a carbon atom through a boron-carbon bond.

The inorganic boron compound is selected from (including but not limited to) boric acid, boric acid esters, boric acid salts, boric acid anhydrides, boron halides. The boric acid may be orthoboric acid, metaboric acid, tetraboric acid. Borates include alkyl and allyl/triorganoborates which hydrolyze in the presence of water to boric acid, e.g. trimethyl borate, triethyl borate, triphenyl borateEsters, tribenzyl borate, tricyclohexyl borate, tris (methylsilyl) borate, tri-tert-butyl borate, tri-n-pentyl borate, tri-sec-butyl borate, DL-menthyl borate, tris (4-chlorophenyl) borate, 2, 6-di-tert-butyl-4-tolyldibutylorthoborate, tris (2-methoxyethyl) borate, benzyldihydroborate, diphenylhydroborate, isopropanolpropanolpinacol borate, triethanolamine borate, and the like. Suitable boric acid anhydrides include those of the formula B₂O₃Typical boron oxides include, but are not limited to, trialkoxyboroxines and derivatives thereof, such as trimethoxyboroxines, triisopropoxyboroxines, 2' -oxybis [4,4, 6-trimethyl-1, 3, 2-dioxaboroxines, and the like. Suitable borates include, but are not limited to, diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, zinc metaborate, tripotassium borate, iron orthoborate salts. Suitable boron halides include, but are not limited to, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, diboron tetrachloride, and the like. Suitable inorganic boron compounds further include partial hydrolyzates of the foregoing borate esters. Typically, the inorganic boron compound is of the formula B₂O₃[ CAS registry number #1303-86-2]Boron oxide or of the formula H₃BO₃[ CAS registry number #10043-35-3]Boric acid of (a). By way of example, suitable inorganic boron compounds are shown below, but the invention is not limited thereto:

the silicon-containing compound containing silicon hydroxyl and/or silicon hydroxyl precursor refers to that the terminal group and/or the side group of the compound contains silicon hydroxyl and/or silicon hydroxyl precursor group. In the present invention, at least a part of the silicon-containing compound must contain the linking group L or can be formed by a suitable reaction. Preferably, the silicon-containing compound contains only one silicon atom per terminal and/or pendant group containing a silicon hydroxyl group and/or a silicon hydroxyl precursor group. Because the skeleton of the linking group L contains carbon atoms, particularly the linking group of the carbon-containing polymer, the dynamic covalent polymer skeleton with rich structure and various performances can be obtained, particularly, the existence of skeleton carbon can conveniently obtain the dynamic covalent polymer with higher mechanical property and printability, and the additional dynamic property can be obtained by conveniently introducing the hydrogen bond action. In addition to the above-mentioned silicon-containing compounds containing a linker L, the other said silicon-containing compounds used to form the B-O-Si bond may be selected from any suitable small or large molecule silicon-containing compound, preferably a polysiloxane, which may be an organic or inorganic polysiloxane compound, including silica.

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-Z) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group, wherein Z 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 (-Z) in the silicon hydroxyl precursor, which can be hydrolyzed to obtain a hydroxyl group, is a functional group.

For the purpose of illustrating the linking group L-containing silicon-containing compound and the linking group L-containing silicon-containing compound that can be formed in the present invention, the following can be exemplified, but the present invention is not limited thereto,

where m, n, x, y, z are the number of repeating units and may be fixed values or average values.

In the present invention, any suitable combination of an inorganic boron compound and a compound containing a silicon hydroxyl group and/or a silicon hydroxyl group precursor may be used to form an inorganic borosilicate linkage, preferably an inorganic boric acid and a silicon hydroxyl group-containing macromolecular compound, an inorganic borate and a silicon hydroxyl group-containing macromolecular compound are used to form an inorganic borosilicate linkage, more preferably an inorganic boric acid and a silicon hydroxyl group-containing macromolecular compound, an inorganic borate and a silicon hydroxyl group-containing macromolecular compound are used to form an inorganic borosilicate linkage, and more preferably an inorganic borate and a silicon hydroxyl group-containing macromolecular compound are used to form an inorganic borosilicate linkage.

In the embodiment of the present invention, the inorganic borono-oxygen bond can be generated in any suitable manner, preferably by dehydration of inorganic boric acid and dealcoholization of inorganic boric acid with organic esters of inorganic boric acid.

In embodiments of the present invention, the dynamic covalent polymer may be formed by forming inorganic borosilicate linkages and optionally inorganic borono linkages, or by preparing a compound containing the inorganic borosilicate linkages and optionally borono linkages and then polymerizing/crosslinking the compound to form the dynamic covalent polymer. In the present invention, one Si atom participating in the formation of B-O-Si on the silicon-containing compound containing the linking group L and the other linking groups may form at most three B-O-Si atoms, which share one Si atom, based on the polyvalent nature of the Si atom. And because the boron atom is a trivalent structure, once the raw material components have proper reactive groups, the inorganic silicon borate and the inorganic boron-oxygen-boron bonds generated in the polymerization process can easily cause the formation of branches and can be further crosslinked.

In embodiments of the present invention, the number of teeth is not limited for the optional supramolecular hydrogen bonds. The number of teeth is the number of hydrogen bonds formed by a hydrogen bond donor (D, i.e., a hydrogen atom) and a hydrogen bond acceptor (a, i.e., an electronegative atom that accepts a hydrogen atom) of the hydrogen bond groups, and each D-a is combined into one tooth (as shown in the following formula, the hydrogen bonding cases of the one-tooth, two-tooth and three-tooth hydrogen bond groups are listed, respectively).

If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond action is weak, and the dynamic covalent polymer mechanical property (modulus and strength) can be improved. If the number of teeth of the hydrogen bond is small, the strength is low, the dynamic property of the hydrogen bond action is strong, and the dynamic property, such as self-repairability, energy absorption characteristic and the like, can be provided together with the dynamic covalent inorganic boric acid silicon ester bond and the inorganic boron oxygen boron bond. In embodiments of the present invention, it is preferred that no more than tetradentate hydrogen bonding is effected, more preferably that no more than tetradentate hydrogen bonding is effected by participation of hydrogen bonding groups on the side groups and/or side chains.

In embodiments of the present invention, the hydrogen bonding group may be a hydrogen bonding group having both a hydrogen bonding acceptor and a hydrogen bonding donor within the same hydrogen bonding group; or part of the hydrogen bond groups contain hydrogen bond donors, and the other part of the hydrogen bond groups contain hydrogen bond acceptors; preferably containing both acceptor and donor.

The hydrogen bond acceptor of the hydrogen bond group in the present invention may be any suitable electronegative atom such as O, N, S, F, and preferably contains at least one of the structures represented by the following general formula (1),

wherein A is selected from oxygen atom and sulfur atom; d is selected from a nitrogen atom and a C-R group; x is a halogen atom; wherein,refers to a linkage to a polymer chain, crosslink or any other suitable group, including a hydrogen atom. Wherein R is selected from hydrogen atom, substituent atom and substituent group.

In the case of the substituent, the number of carbon atoms in R is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10.

When used as a substituent, the structure of R is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure. Among them, the cyclic structure is not particularly limited, and may be selected from an aliphatic ring, an aromatic ring, a sugar ring, and a condensed ring, and an aliphatic ring is preferable.

When the substituent is a substituent, R may or may not contain a hetero atom.

R is selected from hydrogen atom, halogen atom, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted heterohydrocarbyl. Wherein, the substituent atom or the substituent group in R is not particularly limited, and is selected from any one of a halogen atom, a hydrocarbon group substituent group, and a heteroatom-containing substituent group.

R is more preferably a hydrogen atom, a halogen atom, C_1-20Alkyl radical, C_1-20Alkenyl, aryl, arylalkyl, C_1-20Aliphatic heterocarbyl, heteroaryl, heteroaromatic hydrocarbyl, C_1-20Alkoxyacyl, aryloxyacyl, C_1-20An alkylthio acyl group, an arylthio acyl group, or a substituted version of either atom or group.

Specifically, R can be selected from hydrogen atom and fluorineAtom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, allyl group, propenyl group, vinyl group, phenyl group, methylphenyl group, butylphenyl group, benzyl group, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, methylthiocarbonyl group, ethylthiocarbonyl group, phenylthiocarbonyl group, benzylthiocarbonyl group, ethylaminocarbonyl group, benzylaminocarbonyl group, methoxythiocarbonyl group, ethoxythiocarbonyl group, phenoxythiocarbonyl group, benzyloxythiocarbonyl group, methylthiothiocarbonyl group, ethylthiocarbonyl group, phenylthiocarbonyl group, benzylthiocarbonyl group, ethylaminothiocarbonyl group, Benzylaminothiocarbonyl, substituted C_1-20Alkyl, substituted C_1-20Alkenyl, substituted aryl, substituted arylalkyl, substituted C_1-20Aliphatic heterocarbyl, substituted heteroaryl, substituted heteroarylalkyl, substituted C_1-20Alkoxycarbonyl, substituted aryloxycarbonyl, substituted C_1-20Alkylthio carbonyl, substituted arylthio carbonyl substituted C_1-20Alkoxythiocarbonyl, substituted aryloxythiocarbonyl, substituted C_1-20Alkylthio thiocarbonyl, substituted arylthio thiocarbonyl and the like. Wherein, when the related structure has isomers, under the condition of not being specially designated, any isomer can be contained, such as alkyl, under the condition of not being specially designated, the alkyl is formed by losing hydrogen atoms at any position, and specifically, butyl includes but is not limited to n-butyl and tert-butyl; octyl includes, but is not limited to, n-octyl, 2-ethylhexyl. Wherein the substituent atom or substituent is selected from any one of halogen atom, alkyl substituent and heteroatom-containing substituent.

The hydrogen bond donor of the hydrogen bond group in the present invention may be any suitable donor group containing a hydrogen atom, and preferably contains at least one of the structures represented by the following general formula (2),

wherein,refers to a linkage to a polymer chain, crosslink or any other suitable group, including a hydrogen atom.

The structures represented by the general formulae (1) and (2) may be a side group, a terminal group, a chain structure, or the like, or may form a cyclic structure. Wherein the cyclic structure can be a single-ring structure, a multi-ring structure, a spiro structure, a fused ring structure, a bridged ring structure, a nested ring structure, and the like.

In the embodiment of the present invention, the hydrogen bonding group preferably contains both of the structures represented by the general formulae (1) and (2).

In an embodiment of the present invention, the hydrogen bonding group more preferably contains 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 hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, silacarbamate groups, or derivatives thereof, and the like.

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

examples of suitable pendant and terminal hydrogen bonding groups include, but are 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.

In the present invention, the same compound/polymer may contain one or more hydrogen bonding groups, and the same cross-linking network may also contain one or more hydrogen bonding groups, that is, the dynamic covalent polymer may contain a combination of one or more hydrogen bonding groups. The hydrogen bonding group can be on any one or more of the main chain, the side group, the side chain and the branched chain of the linking group L, and can also be on any one or more of the main chain, the side group, the side chain and the branched chain of other linking groups. The hydrogen bonding groups may be formed by any suitable chemical reaction, for example: formed by the reaction between a carboxyl group, an acid halide group, an acid anhydride group, an ester group, an amide group, an isocyanate group and an amino group; formed by the reaction of isocyanate groups with hydroxyl, mercapto, carboxyl groups; formed by the reaction of the succinimide ester group with amino, hydroxyl, mercapto groups.

In the present invention, the content of the hydrogen bonding group and its hydrogen bonding action is not limited. The supramolecular hydrogen bonding may be generated during the formation of polymer components in dynamic covalent polymers; or polymer components in the dynamic covalent polymer can be formed after the supermolecule hydrogen bond is generated in advance; supramolecular hydrogen bonding may also occur during subsequent formation of the dynamic covalent polymer, although the invention is not limited thereto.

In the present invention, there may be other various embodiments, any of which may optionally contain the inorganic boro-oxo-boro-bonding and/or hydrogen bonding, and those skilled in the art can reasonably and effectively implement the present invention according to the logic and context of the present invention.

The invention also provides an energy absorption method, which is characterized in that a dynamic covalent polymer is provided and used as an energy absorption material for absorbing energy, wherein the dynamic covalent polymer contains B-O-Si dynamic covalent bonds, any one B atom is connected with three-O-, and a linking group L is contained in a linking group connected with different Si atoms in at least two B-O-Si dynamic covalent bonds based on different B atoms, and the linking group L contains carbon atoms on the chain skeleton of the dynamic covalent polymer.

In the present invention, the raw material components for preparing the dynamic covalent polymer include other polymers, auxiliaries and fillers which can be added/used in addition to the inorganic boron compound and the silicon-containing compound, and these additives/utilizable substances jointly constitute the dynamic covalent polymer composition by blending with the reaction product of the inorganic boron compound and the silicon-containing compound.

In the embodiment of the present invention, the form of the dynamic covalent polymer or the composition thereof may be a solution, an emulsion, a paste, a common solid, an elastomer, a gel (including a hydrogel, an organic gel, an oligomer swollen gel, a plasticizer swollen gel, an ionic liquid swollen gel), a foam, etc., wherein the content of the low molecular weight component contained in the common solid and the foam is generally not higher than 10 wt%, and the content of the low molecular weight component contained in the gel is generally not lower than 50 wt%. Wherein, the shape and the volume of the dynamic polymer common solid are fixed, the strength is high, the density is large, and the dynamic polymer common solid is suitable for high-strength explosion-proof walls or instrument shells; the elastomer has the general properties of common solids, but has better elasticity and higher softness, and is more suitable to be used as energy-absorbing materials for damping/shock absorption and the like; the dynamic polymer gel has soft texture, better energy absorption performance and elasticity, and is suitable for preparing high-damping energy absorption materials; the dynamic polymer foam material has the advantages of low density, light weight, high specific strength and the like of common foam plastics, and the soft foam material also has good elasticity and energy absorption.

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

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

The mechanical foaming method is that during the preparation of dynamic covalent 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 covalent 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 generating gas and foaming along with chemical reaction in the dynamic covalent polymer foaming process, and generally comprises 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 covalent polymer, three methods of mould pressing foaming molding, injection foaming molding and extrusion foaming molding are preferably adopted to mold the dynamic covalent 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 covalent polymer, a person skilled in the art can select a proper foaming method and a foam material forming method to prepare the dynamic covalent polymer foam material according to the actual preparation situation and the target polymer performance.

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

In embodiments of the present invention, the additional polymers, adjuvants, fillers that may be added/used may be any suitable materials.

The other polymers can be used as additives to improve material performance, endow materials with new performance, improve material use and economic benefits and achieve the effect of comprehensive utilization of the materials in a system. Other polymers may be added/used, 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 is selected from natural high molecular compounds, it can be selected from any one or several of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, etc.

When the other polymer 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 glycol, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polymethyl acrylate, polymethyl methacrylate, polymethacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, polyethylene terephthalate, polyethylene, Ethylene-vinyl acetate copolymers, acrylonitrile-acrylate-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, vinyl chloride-vinyl acetate copolymers, polyvinylpyrrolidone, epoxy resins, phenol resins, urea resins, unsaturated polyesters, and the like.

When the other polymer 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, urethane rubber, epichlorohydrin rubber, thermoplastic elastomer, and the like.

When the other polymer is selected from synthetic fibers, it may be selected from any one or any of the following synthetic fibers: 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, the other polymer is preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polymethyl methacrylate, epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, silicone rubber, polyurethane rubber, or thermoplastic elastomer.

The additive can be added/used, so that the preparation process of the material can be improved, the quality and the yield of the product can be improved, the cost of the product can be reduced, or a certain specific application performance can be endowed to the product. The auxiliary agent is selected from any one or any several of the following auxiliary agents: 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 auxiliary agent can accelerate the reaction rate of reactants in the reaction process by changing the reaction path and reducing the reaction activation energy. In embodiments of the present invention, the catalyst includes, but is not limited to: (1) catalyst for polyurethane Synthesis: amine catalysts, such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N,n, N '-trimethyl-N' -hydroxyethyl bisaminoethyl ether, tetramethyldipropylenetriamine, N-dimethylcyclohexylamine, N '-tetramethylalkylenediamine, N' -pentamethyldiethylenetriamine, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N-dimethylbenzylamine, N-dimethylhexadecylamine, etc.; organic metal catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctoate, lead isooctanoate, potassium oleate, zinc naphthenate, cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, etc. (2) Catalyst for polyolefin Synthesis: such as Ziegler-Natta catalysts, pi-allylnickel, alkyllithium catalysts, metallocene catalysts, diethylaluminum monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, aluminum sesquiethylate, vanadium oxychloride, triisobutylaluminum, nickel naphthenate, rare earth naphthenate, etc. (3) The CuAAC reaction is co-catalyzed by a monovalent copper compound and an amine ligand. The monovalent copper compound may be selected from Cu (I) salts such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; can also be selected from Cu (I) complexes, such as [ Cu (CH)₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Etc.; elemental copper and divalent copper compounds (e.g., CuSO) can also be used₄、Cu(OAc)₂) Generated in situ in the reaction process; among them, the Cu (I) salt is preferably CuBr and CuI, and the Cu (I) complex is preferably CuBr (PPh)₃)₃. The amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amines (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, and the like; among them, TBTA and TTTA are preferable as the amine ligand. (4) thiol-ene reaction catalyst: photocatalysts such as benzoin dimethyl ether, 2-hydroxy-2-methylphenyl acetone, 2-dimethoxy-2-phenylacetophenone and the like; nucleophilic catalyst, e.g. ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropyl-amineEthylamine, and the like. The amount of the catalyst to be used is not particularly limited, but is usually 0.01 to 2% by weight.

The initiator in the auxiliary agent can cause the monomer molecules to be activated to generate free radicals in the polymerization reaction process, so as to improve the reaction rate and promote the reaction to proceed, and the initiator comprises any one or more of the following initiators: organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, the initiator is preferably lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, or potassium persulfate. The amount of the initiator to be used is not particularly limited, but is generally 0.1 to 1% by weight.

the antioxidant in the assistant can retard the oxidation process of polymer samples and ensure that the materials can be successfully prepared and the service life of the materials is prolonged, and comprises any one or more of hindered phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 2,2 ' -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 series hindered phenols such as 1,3, 5-di- [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-triazine, tri-isocyanate hindered phenols such as tri (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate, di-tert-butyl-4-hydroxyphenyl) di-phenylenediamine such as N, N ' -di-tert-butyl-4-hydroxyphenyl (BHT, N ' -di-tert-butyl-4-hydroxyphenyl) propionate, N-tert-butyl-4-hydroxyphenyl) phosphite, N-tert-butyl-4-butyl-tert-butyl-4-tert-butyl-tert-phenyl phosphite, BHT, N-butyl-4-hydroxy-phenyl phosphite, N-tert-butyl-4-phenyl phosphite, N-butyl-4-butyl-4-phenyl phosphite, N-butyl-phenyl phosphite, N-tert-butyl-4-tert-butyl-4-butyl-phenyl phosphite, N-butyl-4-tert.

The light stabilizer in the assistant can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and the assistant comprises any one or more than one 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 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, dimethyl tin isooctyl dimercaptoacetate, dimethyl tin dimercaptolate, and combinations thereof; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; polyols, such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; 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 auxiliary agent 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: polyhydric alcohol chain extenders such as ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), resorcinol dihydroxyethyl ether (HER), p-bis-hydroxyethyl bisphenol a; 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 (DETDA), 1,3, 5-triethyl-2, 6-diaminobenzene (TEMPDA); chain extenders of the alcamines type, such as triethanolamine, triisopropanolamine, N' -bis (2-hydroxypropyl) aniline. The amount of the chain extender to be used is not particularly limited, and is generally 1 to 20% by weight.

The toughening agent in the auxiliary agent 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 a 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 and polyols, such as stearyl alcohol, cetyl alcohol, pentaerythritol; 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 auxiliary agent can make the polymer sample easy to release, and has smooth and clean surface, and the auxiliary agent comprises 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, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber and the like; among them, the release agent is preferably dimethyl silicone oil or polyethylene glycol. 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 auxiliary agent 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 auxiliary agent comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl 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, e.g. epoxy glycolsThe raw materials comprise oil esters, epoxy fatty acid monoesters, epoxy tetrahydrophthalic acid esters, epoxy soybean oil, epoxy stearic acid (2-ethyl) hexyl ester, epoxy soybean oleic acid 2-ethylhexyl ester, 4, 5-epoxy tetrahydrophthalic acid di (2-ethyl) hexyl ester and buxus sinica acetyl ricinoleic acid methyl ester; 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, dipentaerythritol 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 auxiliary agent 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 adjuvant can improve the dynamic property of the dynamic polymer so as to obtain the optimal desired performance, and is generally a compound which has a free hydroxyl group or a free carboxyl group or can give or accept an electron pair, including but not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, Lewis base 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, polyoxyethylene alkyl ether alcohol 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 alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene phosphoric acid ether esters, glycerin mono fatty acid esters; high molecular antistatic agents such as ethylene oxide-propylene oxide adduct of ethylenediamine, 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, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (antistatic agent SN), 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 adjuvant can improve the surface tension between various constituent phases in the polymer mixed solution containing the adjuvant to form a uniform and stable dispersion system or emulsion, and is preferably used for emulsion polymerization/crosslinking, 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, fatty alcohol sulfate salts, castor oil sulfate ester salts, sulfated butyl ricinoleate 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 fatty alcohol polyoxyethylene ether, alkylphenol ethoxylates, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol amine fatty acid amide, etc.; 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 dispersing agent in the auxiliary agent 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 can prevent the particles from settling and coagulating to form a stable suspension, and the dispersing agent comprises any one or more of the following dispersing agents: 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; 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 comprises any one or more 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 auxiliary agent can enable the dyed materials 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 auxiliary agent can diffuse and reflect incident light to generate low-gloss matte and matte appearance when the incident light reaches the surface of the polymer, 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 auxiliary agent can increase the flame resistance of the material, and includes but is not limited to any one or any several 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, dibenzylidene sorbitol and derivatives thereof, ethylene propylene rubber, ethylene propylene diene monomer and the like; among them, the nucleating agent is preferably silica, dibenzylidene sorbitol (DBS), 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 auxiliary agent can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevents the solid particles from settling during storage, and can 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, aluminum alkoxides, titanium chelates, aluminum chelates; organic compounds such as organobentonite, hydrogenated castor oil/amide wax, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose ester, 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 auxiliary agent 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 the production, storage and use processes, 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 monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine, titanate coupling agents; high molecular substances such as bentonite, artificial hectorite, micro-powder silica, colloidal aluminum, animal protein, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, crotonic acid copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, etc.; among them, coconut oil diethanolamide and acrylic acid-methacrylic acid copolymer are preferable as the thickener. 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 auxiliary agent can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the auxiliary agent comprises any one or more of the following leveling agents: polydimethyl siloxane, polymethylphenyl siloxane, polyacrylates, silicone resins, and the like; among them, polydimethylsiloxane and polyacrylate are preferable as the leveling agent. 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 covalent polymer, the auxiliary agent is preferably selected from a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a chain extender, a toughening agent, a plasticizer, a foaming agent, a flame retardant and a dynamic regulator.

② the ② filler ② mainly ② plays ② the ② following ② roles ② in ② a ② dynamic ② covalent ② polymer ②, ② namely ② ① 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 adjusting 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 photostability ② and ② chemical ② corrosion ② resistance ②, ② playing ② a ② role ② in ② increasing ② the ② volume ②, ② ① 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 is selected from any one or any several of the following fillers: inorganic non-metal filler, metal filler and organic filler.

The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, china clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, carbon nanotubes, molybdenum disulfide, slag, flue dust, wood powder and shell powder, diatomite, 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, boron 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 includes, but is not limited to, any one or any several of the following: powders, nanoparticles and fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof.

The organic filler includes, but is not limited to, any one or any several of the following: fur, natural rubber, asbestos, shellac, chitin, chitosan, protein, raw lacquer, shell powder, silk, rayon, phenolic microbeads, resin microbeads, and the like.

The type of the 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, chitosan, protein, and resin beads are preferred, and the amount of the filler used is not particularly limited, and is generally 1 to 30 wt%.

In the preparation process of the dynamic covalent polymer, the dynamic covalent 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 covalent 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 covalent polymer, other polymers, auxiliaries and fillers which can be added/used as described above can be added to form a dynamic covalent polymer composite system, but the addition/use of the other polymers, auxiliaries and fillers is not required.

The specific method for preparing dynamic covalent polymers by solution stirring mixing is generally to mix the raw materials in dissolved or dispersed form in respective solvents or common solvents in a reactor by stirring. 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 polymer samples in the forms of solution, emulsion, paste, jelly and the like, or the solvent can be selectively removed to prepare solid polymer samples in the forms of film, block, foam and the like. When the dynamic covalent polymer is prepared by the method, an initiator is added into a solvent according to the circumstances to initiate the polymerization in a solution polymerization mode to obtain the dynamic covalent polymer, or a dispersing agent and an oil-soluble initiator are added to prepare a suspension to initiate the polymerization in a suspension polymerization or slurry polymerization mode to obtain the dynamic covalent polymer, or an initiator and an emulsifying agent are added to prepare an emulsion to initiate the polymerization in an emulsion polymerization mode to obtain the dynamic covalent 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, methanol, ethanol, chloroform, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, N-butyl acetate, trichloroethylene, mesitylene, dioxane, Tris buffer, citric acid buffer, ethyl acetateAcid buffer solution, phosphoric acid buffer solution, boric acid buffer solution, 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 polyethylene glycol oligomer, 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 covalent polymer is prepared by deionized water and is selected to be reserved, the hydrogel can be obtained; preparing a dynamic covalent polymer by using an organic solvent, and obtaining organogel when the dynamic covalent polymer is selected to be reserved; preparing dynamic covalent polymer by using oligomer and obtaining oligomer swelling gel when selecting to reserve the dynamic covalent polymer; when the plasticizer is used for preparing the dynamic covalent polymer and the dynamic covalent polymer is selected to be reserved, the plasticizer swelling gel can be obtained; when the ionic liquid is used for preparing the dynamic covalent polymer and the dynamic covalent 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 covalent polymer by melt stirring and mixing is to directly stir and mix the raw materials in a reactor or 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 lower 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. In the preparation of dynamic covalent polymers in this way, it is generally necessary to initiate the polymerization by melt polymerization or gas phase polymerization, optionally with the addition of small amounts of initiator, to give dynamic covalent polymers. 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 covalent 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 ℃, 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 covalent polymer, the molar equivalent ratio of the selected inorganic boron compound and the siloxane compound containing silicon hydroxyl groups is in a proper range, and the molar equivalent ratio of other reactive groups for polymerization/crosslinking reaction is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, and more preferably in the 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 covalent polymer, the amount of the raw materials of each component of the dynamic covalent polymer is not particularly limited, and can be adjusted by those skilled in the art according to the actual preparation situation and the target polymer performance.

The dynamic covalent polymer has adjustable performance in a large range, and has wide application prospect in the fields of military and aerospace equipment, functional coatings and coatings, biomedical materials, energy, buildings, bionics, intelligent materials and the like.

By utilizing the dilatancy of the dynamic covalent polymer, the polymer can be applied to the aspects of oil extraction of oil wells, fuel oil explosion prevention and the like, and can also be used for preparing speed lockers of roads and bridges. When the polymer material is vibrated, a large amount of energy can be dissipated to play a damping effect, so that the vibration of a vibrator is effectively alleviated, and the polymer material can be applied to manufacturing of damping shock absorbers and is used for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings; the material is used as an energy-absorbing buffer material and is 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 objects or human bodies under the action of external force, including shock waves generated by explosion and the like, are reduced; as energy-absorbing materials, sound insulation, noise elimination and the like can be performed; the method can also be used for manufacturing an anti-seismic shear plate or a cyclic stress bearing tool, or used for manufacturing a stress monitoring sensor. The dynamic covalent bond and the intensity and the dynamic difference of the supermolecule hydrogen bond can be used as a shape memory material; the stress-sensitive polymer material is prepared through the dynamic reversibility and stress rate dependence of the dynamic covalent polymer, and part of the stress-sensitive polymer material can be applied to preparing toys and body-building materials with magic effects of fluidity and elastic conversion. When the inorganic silicon borate ester bond is used as a sacrificial bond, the inorganic silicon borate ester 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 inorganic silicon borate ester bond can be widely applied to the fields of military affairs, aerospace, sports, energy sources, buildings and the like.

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

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

Example 1

Oligomeric polymethylhydrosiloxane (PHMS, molecular weight 500) and acryloyloxy eicosyl trimethoxy silane are mixed, the ratio of the mole number of active hydrogen atoms (hydrogen atoms directly connected with Si) in the polymethylhydrosiloxane to the mole number of acryloyloxy methyltrimethoxy silane double bonds in the reaction is controlled to be about 1:1, chloroplatinic acid is used as a catalyst to carry out addition reaction, and the organopolysiloxane with trimethoxy silicon groups on the side groups is prepared.

The organopolysiloxane, hydroxyl-terminated polydimethylsiloxane (molecular weight 700) and trimethyl borate are reacted in the presence of Si-OCH₃Mixing the groups, Si-OH groups and B-OR groups in a molar ratio of 1:1:2, heating to 80 ℃, uniformly mixing, adding 4ml of deionized water into 100g of the mixture, dropwise adding a small amount of acetic acid, adding 1.0g of graphene and 0.5g of organic bentonite, and carrying out polymerization reaction under a stirring state to prepare the dynamic polymer containing inorganic borate silicone bonds.

The obtained polymer sample is rubbery, can be stretched in a large range at a slow stretching speed and generates creep deformation; the recovery is slow or can not be realized after the finger is lightly pressed; but exhibit elastic characteristics if stretched or tapped rapidly. Because the conductivity of the sensor can sensitively respond to the pressure or the pulling force, the sensor is suitable for being used as a force sensor.

Example 2

Mixing methoxy-terminated polymethylvinylsiloxane (molecular weight is about 20000) with 2-tert-butoxycarbonylaminoethanethiol and 3-mercaptopropyltrimethoxysilane according to the molar ratio of a double bond to a compound of two sulfydryl groups of 3:2:1, adding 0.2 wt% of photoinitiator benzoin dimethyl ether (DMPA) relative to 2-tert-butoxycarbonylaminoethanethiol, fully stirring, and placing in an ultraviolet crosslinking instrument for ultraviolet radiation for 4 hours to obtain the organopolysiloxane containing side hydrogen bond groups.

The above-mentioned organopolysiloxanes containing pendant hydrogen bonding groups, 1, 7-dichlorooctamethyltetrasiloxane and 2, 6-di-tert-butyl-4-tolyldibutylboronate as Si-OCH₃Mixing the groups, the Si-Cl groups and the B-OR groups in a molar ratio of 1:1:2, heating 100g of the mixture to 80 ℃, uniformly mixing, adding 4.2g of microsphere foaming agent, 2g of ammonium polyphosphate and 4ml of deionized water, rapidly stirring for 30s, uniformly mixing, and continuously stirring in a nitrogen atmosphere for reaction for 4h to prepare the soft hair containing the side hydrogen bond groups and the borosilicate silicon ester bondsA foamed silicone material.

Pouring the reactant into a proper mould, placing the mould in a vacuum oven at 60 ℃ for continuous reaction for 24h, cooling to room temperature, placing for 30min, and carrying out foaming 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, and the sample can be expanded within a certain range and has a good self-repairing function, can be used as self-repairing glass interlayer adhesive and has durability.

Example 3

Bis (3-methoxydiethylsilylpropyl) (Z) -but-2-enedioate and ethoxyboric acid were mixed in a molar ratio of 1:1, 100g of the mixture was taken, heated to 80 ℃ and 10ml of deionized water was added to conduct polymerization under stirring to prepare a dynamic polymer containing a borosilicate silicone bond.

The product shows good dilatancy and good energy absorption effect, and can be used as a toy with magic elasticity.

Example 4

Mixing boric acid and propenyl dimethylchlorosilane according to the molar ratio of 1:3, and reacting for 12 hours at 80 ℃ by using triethylamine as a catalyst to obtain a silicon borate compound 4 with a double bond at the tail end.

Dissolving ethyl isocyanate and propylene glycol monoallyl ether with an equivalent molar weight in dichloromethane, and obtaining (allyloxy) propyl ethyl carbamate under the catalysis of triethylamine.

20g of polyether dithiol, 6.8g of the above-mentioned silyl borate compound having a double bond at the terminal, 3.2g of the above-mentioned (allyloxy) propylethylcarbamate were charged in a three-necked flask, and then placed in an ultraviolet crosslinking apparatus and irradiated with ultraviolet for 8 hours to obtain a dynamic polymer having a pendant hydrogen bonding group and a silyl borate bond.

The polymer product can be slowly extended under the action of external tensile stress, and a super extension effect (the elongation at break can reach 3000%) is obtained. 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 5

limonene oxide extracted from orange peel and 100psi carbon dioxide are polymerized under the catalysis of β -diimine zinc to obtain the polycarbonate PLimC.

Mixing the polycarbonate PLimC, gamma-mercaptopropylmethyldimethoxysilane and N- [ (2-mercaptoethyl) carbamoyl ] propionamide according to the proportion of double bond groups to mercapto groups of 10:5:5, adding 0.3 wt% of AIBN, and carrying out click reaction to obtain the polycarbonate with the side group containing hydrogen bond groups and methoxy silane groups.

Weighing 45g of the polycarbonate with the side group containing the hydrogen bond group and the methoxysilane group and 10g of tris (2-methoxyethyl) borate, fully stirring and uniformly mixing, heating to 80 ℃, adding 10ml of deionized water, dropwise adding a small amount of acetic acid, then adding 2.5g of polymer foaming microspheres and 0.2mg of BHT antioxidant, quickly stirring by professional equipment until bubbles are generated, then quickly injecting into a mold, curing at room temperature for 30min, and then curing at 80 ℃ for 4h to obtain the foam material containing the side hydrogen bond group and the borosilicate silicone bond.

The foam material has good chemical resistance, can be used as a substitute of glass products, a rigid packaging box and a decorative plate, has toughness and durability, and has good self-repairing property and biodegradability.

Example 6

Mixing dimethylallyl chlorosilane and 1, 10-decanedithiol according to a molar ratio of 2:1, taking AIBN as an initiator and triethylamine as a catalyst, and carrying out a thiol-ene click reaction to obtain the dimethylallyl chlorosilane end-capped silicon-containing compound.

Mixing the silicon-containing compound and boric acid according to the molar ratio of 1:2, fully stirring and uniformly mixing, taking 100g of the mixture, heating to 80 ℃, adding 4ml of deionized water, and carrying out polymerization reaction for 8h under the stirring state to prepare the dynamic polymer containing boron-oxygen-boron bonds and silicon borate ester bonds.

The polymer product has good dilatancy and can be used as a material of a speed locker.

Example 7

(1) Oligomeric polyvinyl alcohol (PVA) (molecular weight is about 500) and a certain amount of 3-isocyanate propyl trimethoxy silane are mixed and reacted in dichloromethane by taking triethylamine as a catalyst, and the ratio of the mole number of hydroxyl groups of the PVA to the mole number of isocyanate groups in the reaction is controlled to be about 1:1.2, so that polyol oligomer with a side group containing a carbamate group and a trimethoxy silicon group is obtained.

The above polyol oligomer having a urethane group and a trimethoxy silicon group as a pendant group and boric acid are in accordance with Si-OCH₃Mixing the groups and B-OH groups in a molar ratio of 1:1, heating to 80 ℃, uniformly mixing, then dropwise adding a small amount of 20% acetic acid solution, carrying out polymerization reaction for 8 hours under a stirring state, then adding 80 wt% of epoxidized soybean oil and 3 wt% of carbon nano tubes, stirring, fully swelling for 24 hours, and preparing the epoxidized soybean oil containing side hydrogen bond groups and borosilicate silicon ester bondsSoybean oil swollen dynamic polymer organogels.

In the embodiment, the polymer organogel not only shows better mechanical properties, but also has functional characteristics of self-repairing, pH response and the like. The prepared organogel has excellent toughness.

Example 8

20g of four-arm PEG (molecular weight is about 25000) with trimethoxy silicon group at the tail end and 3.2g of diphenylhydroborate are mixed, heated to 80 ℃, stirred uniformly, added with 4ml of deionized water, and subjected to polymerization reaction under the stirring state to prepare the dynamic polymer containing the borate silicone bond.

The dynamic polymer is further swelled by deionized water, and the dynamic polymer hydrogel can be obtained. The dynamic polymer hydrogel has excellent self-repairing property and can be used as an aqueous medical dressing.

Example 9

Using allyl alcohol as an initiator and stannous octoate as a catalyst to initiate epsilon-caprolactone ring-opening polymerization to obtain olefin single-end-capped polycaprolactone, esterifying the olefin single-end-capped polycaprolactone with acrylic acid to obtain olefin double-end-capped polycaprolactone, reacting the olefin double-end-capped polycaprolactone with gamma-mercaptopropyl trimethoxy silane by using AIBN as an initiator and triethylamine as a catalyst, and performing a thiol-ene click reaction to obtain the trimethoxy silane end-capped polycaprolactone.

The silane trimethoxy silane terminated polycaprolactone and trimethyl borate are Si-OCH₃Mixing the groups and the B-OR group in a molar ratio of 1:1, taking 20g of the blend, heating to 80 ℃, uniformly mixing, adding 4mL of deionized water, adding 1mL of triethylamine and 200mg of 200-mesh nano clay, and carrying out polymerization reaction under a stirring state to prepare the dynamic polymer containing the borosilicate silicone bond.

The polymer samples produced can be stretched to a certain extent. In addition, after the surface of the sample is subjected to small scratches and placed in a mold at 50 ℃ to apply certain pressure for attaching for 2 hours, the scratches disappear, and the self-repairing effect is good. The polymer product can be used as a packaging material with scratch resistance and degradability.

Example 10

Hydroxyethyl acrylate is used as a monomer, and the polyhydroxyethyl acrylate (with the molecular weight of about 800) is prepared through free radical polymerization.

The oligomeric polyhydroxyethyl acrylate, 2-furfuryl isothiocyanate and 3-isocyanatopropyl trimethoxy silane are mixed (the molar ratio of hydroxyl to isocyanate is 2:1.1:1.1), triethylamine is used as a catalyst, and the reaction is carried out in dichloromethane, so as to prepare the polyacrylate with the side group containing thiocarbamate groups and trimethoxy silane groups.

Polyacrylate and boric acid having a thiocarbamate group and a trimethoxy-silyl group as pendant groups, as described above, in the form of Si-OCH₃Mixing the groups and the B-OH groups in a molar ratio of 1:1, heating to 80 ℃, uniformly mixing, adding 2g of white carbon black, 3g of titanium dioxide, 1.5g of cellulose microcrystal and 2.2g of ferric oxide, and carrying out polymerization reaction for 8 hours under a stirring state to obtain the dynamic polymer containing the side hydrogen bond groups and the silicon borate ester bonds.

The polymer product can be used for preparing a polymer gasket or a polymer plate with a self-repairing function.

Example 11

Styrene and styrene ethyl trimethoxy silane are mixed according to the molar ratio of 2:1, AIBN is used as an initiator, and the polystyrene containing the terminal siloxane modification is prepared by free radical copolymerization. 15g of the above-mentioned terminal siloxane-modified polystyrene and 3.2g of trimethyl borate were weighed into a dry clean beaker, 120ml of a toluene solvent was poured therein, and after heating to 60 ℃ and dissolution by stirring, the mixed solution was placed in a suitable mold and dried in a vacuum oven at 60 ℃ for 24 hours to finally obtain a hard block polymer solid.

The product has higher surface hardness and good mechanical strength, is put into a die to be heated to 180 ℃, is molded for 5min under the pressure of 5MPa, is made into a dumbbell-shaped sample strip with the size of 80.0 multiplied by 10.0 multiplied by 4.0mm, is subjected to tensile test by a tensile testing machine with the tensile rate of 10mm/min, and has the tensile strength of 8.34 +/-2.18 MPa and the tensile modulus of 19.45 +/-2.57 MPa, good chemical resistance and capability of using the prepared polymer material as a substitute of glass products and a hard packing box.

Example 12

(1) 3-aminopropyl methyl dimethoxy silane and adipoyl chloride are mixed according to the molar ratio of 2:1, triethylamine is used as a catalyst, and the mixture reacts in anhydrous dichloromethane to prepare the disiloxane end-capped compound.

8.0g of the above-mentioned disiloxane end-capping compound and 2.5g of boric acid were weighed, heated to 60 ℃ and reacted for 8 hours with stirring to obtain a dynamic polymer containing a borosilicate linkage and a boroxyboron linkage as the 1 st network polymer.

(2) Allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidinone were dissolved in toluene in a molar ratio of 1:1, and potassium carbonate was used as a catalyst and tetrabutylammonium bromide was used as a phase transfer agent to give an oxazolidinone group-containing olefin monomer 12 a.

Under the anhydrous and oxygen-free conditions, allyl mercaptan and 2-thiophene isocyanate are dissolved in dichloromethane according to the molar ratio of 1:1, and are catalyzed by triethylamine to obtain the olefin monomer 12b containing thiocarbamate groups.

Olefin monomer 12a and olefin monomer 12b are fully mixed according to the molar ratio of 50:50, 80 parts of epoxidized soybean oil is added, after the mixture is fully mixed by stirring, the mixture is swelled in the 1 st network polymer, 5mol percent of AIBN is added, and the epoxidized soybean oil swelled dynamic polymer organogel containing side hydrogen bond groups, borosilicate silicon bonds and boron-oxygen-boron bonds is prepared by free radical polymerization.

The epoxidized soybean oil swollen dynamic polymer organogel has soft elasticity and can be used for manufacturing an energy absorbing material.

Example 13

Mixing 25g of polyethylene glycol with one end being silicon hydroxyl end-capped (molecular weight is about 5000), 2g of polyethylene glycol with two ends being silicon hydroxyl end-capped (molecular weight is about 2000) and 2.2g of trimethyl borate, heating to 80 ℃, uniformly mixing, adding 10mL of deionized water and 100mg of nano silicon dioxide with the particle size of 25nm, ultrasonically dispersing for 1h, and carrying out polymerization reaction for 8h under the stirring state to obtain the non-crosslinked dynamic polymer containing the silicon borate bond and the boron-oxygen-boron bond.

The polymer product can be used as an additive of lubricating oil and is used for prolonging the service life of the lubricating oil.

Example 14

Polybutadiene with siloxane groups on side groups is prepared by mixing polybutadiene and mercaptomethyl diethoxysilane, keeping the molar ratio of alkenyl to mercapto to be 5:1, using DMPA as a photoinitiator and ultraviolet light as a light source through click reaction. 18g of the polybutadiene containing siloxane groups in the side groups and 4.7g of tris (4-chlorophenyl) borate are weighed, heated to 60 ℃ and dissolved by stirring, and then a small amount of 20% acetic acid aqueous solution is added to continue the reaction for 4 hours, so that a dynamic polymer containing a silicon borate bond is obtained.

The polymer product can be used for preparing polymer plugging glue with good plasticity and can be recycled and repaired.

Example 15

3-chloropropyldimethylmethoxysilane and boric acid are mixed according to an equal molar ratio, heated to 60 ℃, stirred and dissolved, and then a small amount of water is added for reaction for 3 hours to obtain a boric acid compound containing a boric acid silicon ester bond.

Mixing 4,4' -disilenol and the boric acid compound containing the borosilicate silicone bond according to an equimolar ratio, taking 30g of the mixture, heating to 80 ℃, adding 10mL of deionized water and 1.5g of graphene oxide, and continuing to react for 8h to obtain the non-crosslinked dynamic polymer containing the borosilicate silicone bond.

The polymer product can be used for preparing an adhesive with a self-repairing function.

Example 16

Mixing trimethyl borate and dimethyl methoxy-3-butene silane according to a molar ratio of 1:3, heating to 60 ℃, stirring to dissolve, adding a small amount of water, and continuing to react for 4 hours to obtain the trivinyl compound containing the borate silicon ester bond.

Mixing the trivinyl compound containing the borosilicate silicone bond and trimethylolpropane tri (2-mercaptoacetate) according to a molar ratio of 1:1, and placing the mixture in an ultraviolet crosslinking instrument for ultraviolet radiation for 8 hours to obtain the dynamic polymer containing the borosilicate silicone bond.

The polymer product can be used as a sheet or a coating with self-repairing and recyclable functions.

Example 17

BPO is used as an initiator, and methyl vinyl diethoxy silane and low-density polyethylene are subjected to grafting reaction to prepare silane grafted polyethylene.

Weighing 5g of trimethyl borate, 65g of silane grafted polyethylene (molecular weight is about 6000), 35g of low-density polyethylene, 8g of decabromodiphenylethane, 2g of antimony trioxide, 1g of polytetrafluoroethylene anti-dripping agent, 1.0g of dicumyl peroxide, 1g of stearic acid, 0.2g of antioxidant 1010, 0.2g of di-n-butyltin dilaurate and 0.5g of dimethyl silicon oil, uniformly mixing, heating to 150 ℃, pressurizing to 15MPa, molding for 15min, placing the prepared sample piece in 90 ℃ water for reaction for 2h, taking out, placing in a mold, placing under the protection of 120 ℃ nitrogen for 4h, and drying to obtain the polyethylene base material containing the borosilicate silicone bond.

The polymer product can be reshaped, and exhibits recyclability. And has excellent comprehensive performance, shows good mechanical strength and impact resistance, and can be used as an impact resistant 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 covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-atoms and wherein the linking group to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms comprises a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

2. A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein the linking group to a different Si atom of at least two B-O-Si dynamic covalent bonds based on different B atoms is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

3. A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein the linking group bonded to any different Si atom of at least two different B-O-Si dynamic covalent bonds is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

4. A dynamic covalent polymer comprising B-O-Si dynamic covalent bonds wherein any one B atom is bonded to three-O-s, and wherein any divalent and higher than divalent linking group bonded to a Si atom in any different B-O-Si dynamic covalent bond is a linking group L comprising carbon atoms in the backbone of the dynamic covalent polymer backbone.

5. The dynamic covalent polymer of any of claims 1 to 4 further comprising a B-O-B bond.

6. The dynamic covalent polymer of any of claims 1 to 4, further comprising hydrogen bonding in its composition or compositions comprising it.

7. The dynamic covalent polymer according to any of claims 1 to 4, characterized in that it or the composition containing it has any of the following properties: solutions, emulsions, creams, gels, ordinary solids, elastomers, foams.

8. The dynamic covalent polymer of any of claims 1 to 4, wherein the formulation components of which further comprise any one or any of the following additives: other polymers, auxiliaries, fillers;

wherein, the other polymer is selected from any one or more of the following polymers: natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers;

wherein, the auxiliary agent is selected from any one or more of the following components: 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 is selected from any one or more of the following materials: inorganic non-metal filler, metal filler and organic filler.

9. The dynamic covalent polymer according to any of claims 1 to 4, characterized in that it is applied to: the composite material comprises a shock absorber, a buffer material, a sound insulation material, a silencing material, an impact-resistant 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, a toy and a force sensor.

10. A method for absorbing energy, characterized in that a dynamic covalent polymer is provided and used as an energy absorbing material for absorbing energy, wherein the dynamic covalent polymer comprises B-O-Si dynamic covalent bonds, any B atom of the dynamic covalent polymer is connected with three-O-, and the linking groups connected with different Si atoms of at least two B-O-Si dynamic covalent bonds based on different B atoms comprise linking groups L, and the linking groups L comprise carbon atoms on the backbone of the dynamic covalent polymer.