WO2018137504A1

WO2018137504A1 - Dynamic covalent polymer and application thereof

Info

Publication number: WO2018137504A1
Application number: PCT/CN2018/072454
Authority: WO
Inventors: 郭琼玉; 徐晖; 张欢; 梁愫; 林淦; 欧阳勇; 翁文桂
Original assignee: 翁秋梅
Priority date: 2017-01-25
Filing date: 2018-01-12
Publication date: 2018-08-02
Also published as: CN108359100A

Abstract

A dynamic covalent polymer, the same comprising a dynamic covalent inorganic ester linkage of silicon borate, wherein a connecting group which is connected to silicon atoms in at least two different inorganic ester linkages of silicon borate contains a carbon atom which is on the dynamic covalent polymer chain. The dynamic covalent polymer has strong dynamic reversibility and energy dissipation due to containing the inorganic ester linkage of silicon borate, and exhibits stimuli-responsiveness, self-reparation and like functional properties, thus having a wide range of application prospects in the fields of athletic therapy, functional coatings, biomimetic materials, and the like.

Description

Dynamic covalent polymer and its application

Technical field

The invention relates to the field of smart polymers, in particular to a dynamic covalent polymer composed of dynamic covalent bonds and an application thereof.

Background technique

Conventional polymers generally consist of ordinary covalent bonds. Due to the high bond energy and thermal stability of ordinary covalent bonds, polymers have good stability and mechanical properties as well as lack of dynamics. Dynamic polymers are a new class of polymer systems formed by dynamic chemical bonds. Dynamic polymers can be classified into physical dynamic polymers based on supramolecular forces and covalent dynamic polymers based on dynamic covalent bonds, depending on the dynamic chemical bonds in the dynamic polymer. The covalent dynamic polymer constructed by the dynamic reversible covalent bond has remarkable characteristics due to the special properties of the dynamic reversible covalent bond.

A dynamic covalent bond is a type of chemical bond that can undergo a controlled reversible reaction under certain conditions. It is a relatively weak covalent bond than a non-covalent bond. It can be achieved by changing external conditions or spontaneously. Dynamic rupture and formation of valence bonds. The introduction of dynamic covalent bonds into polymers is a viable method for forming novel dynamic polymers. However, common dynamic covalent bonds such as Dears-Alder reaction products, nitrogen oxides, etc. often need to be broken at high temperatures, and the side reactions are severe. How to obtain a system with strong dynamic performance, controllability and wide application range is still a difficult problem in the prior art.

Summary of the invention

The present invention is directed to the above background, and provides a dynamic covalent polymer which exhibits excellent dynamic reversibility and which exhibits stimuli responsiveness, plasticity, self-healing property, recyclability, Functional characteristics such as reworkability.

The invention is implemented by the following technical solutions:

A dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is linked to three -O-, and wherein at least two BO-Si based on different B atoms are dynamic The linking group to which the different Si atoms in the covalent bond are bonded contains a linking group L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is linked to three -O-, and wherein at least two BO-Si based on different B atoms are dynamic The linking group to which the different Si atoms in the covalent bond are bonded is a linking group L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is linked to three -O-, and wherein at least two different BO-Si dynamic covalent bonds are present The linker to which any of the different Si atoms are bonded is a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.

A dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is bonded to three -O-, and wherein any different BO-Si dynamic covalent bond is in Si Any divalent and divalent or higher linking group attached to the atom is a linking group L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.

Wherein, the linking group L may be a low molecular weight or high molecular weight backbone having a carbon atom in the skeleton, preferably a polymer linking group having a molecular weight of more than 1000 Da, and more preferably having a carbon atom of not less than a skeleton. A polymer linkage having a molecular weight of 20 greater than 1000 Da. The linker L also contains optional heteroatoms and/or elemental atoms which can form an elemental organic group. The linker L can 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-type, 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 linker L can have any one or more glass transition temperatures.

According to an embodiment of the present invention, a dynamic covalent polymer may contain different linking groups L; in addition to the linking group L, some other linking groups may be added to connect different Si atoms in different BO-Si, preferably (poly Silicone; the other linkers may also have any suitable topology.

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

The dynamic covalent polymer or its composition described in the present invention may optionally further comprise a supramolecular hydrogen bond, wherein the supramolecular hydrogen bonding may be intrachain/intramolecular non-crosslinking (intrachain formation) Ring) and/or interchain/intermolecular crosslinks and/or interchain/intermolecular non-crosslinking (polymerization).

In an embodiment of the invention, the dynamic covalent polymer or a composition thereof may be in the form of a solution, an emulsion, a paste, a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer). Swelling gel, plasticizer swelling gel, ionic liquid swelling gel), foam, and the like.

In an embodiment of the present invention, the dynamic covalent polymer may be selectively blended with other polymers, auxiliaries, and fillers that may be added/used during the preparation to form a dynamic covalent polymer.

The present invention also provides a method of absorbing energy, characterized in that a dynamic covalent polymer is provided and energy is absorbed as an energy absorbing material, wherein the dynamic covalent polymer contains BO-Si dynamic covalent a bond in which any one of the B atoms is bonded to three -O-, and wherein the linking group which is bonded to at least two different Si atoms in the BO-Si dynamic covalent bond based on different B atoms contains a linking group L, The linker L described contains a carbon atom on the backbone of the dynamic covalent polymer backbone.

In the embodiment of the present invention, the dynamic covalent polymer has a wide range of properties and has broad application prospects. Specifically, it can be applied to fabricate shock absorbers, cushioning materials, soundproof materials, and sound absorbing. Materials, impact protection materials, sports protection products, military and police protective products, self-healing coatings, self-healing sheets, self-healing adhesives, bulletproof glass interlayer adhesives, energy storage device materials, ductile materials, shape memory materials , toys and other products.

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

(1) In the present invention, at least a part of the inorganic boronic acid silicide bond has a carbon atom on the linking group, that is, at least a part of the polymer chain is a carbon-containing chain, and the advantages of the carbon-containing chain polymer can be fully utilized, including It is not limited to chemical structure, rich in topology, rich in performance, can create specific dynamic covalent polymers, has more freedom than the prior art, has more excellent performance and wider than existing materials. use.

(2) In the present invention, an inorganic boric acid ester bond and a partially optional inorganic boron boron bond are used as dynamic covalent bonds to construct a dynamic covalent polymer, and optionally contain hydrogen bonding, which fully utilizes inorganic boric acid. The dynamics of silicon ester bonds and supramolecular hydrogen bonds provide dynamic covalent polymers with specific properties such as fast self-healing, sensitive stress/strain response. Compared to supramolecular polymers, the dynamic covalent polymers have stronger dynamic bond energy and different stimuli responsiveness, showing specificity. Since there is no common covalent cross-linking in the dynamic covalent polymer, the material can be completely self-repairing, shaping, recycling and reprocessing.

(3) The dynamic covalent polymer of the present invention has a rich structure and various properties, and the dynamic covalent component and the supramolecular component contained therein are controllable. By adjusting the number of functional groups in the starting compound, the molecular structure, the molecular weight, and/or introducing a reactive group, a group that promotes dynamics, a functional group, and/or a composition of the raw material in the raw material compound, Dynamic covalent polymers with different structures can be prepared, so that the dynamic covalent polymers can exhibit a variety of properties to meet the application needs of different occasions.

(4) Dynamic reversible bonds in dynamic covalent polymers have strong dynamic reactivity and mild dynamic reaction conditions. Compared with other existing dynamic covalent systems, the present invention makes full use of the excellent thermal stability and high dynamic reversibility of the inorganic boronic acid silicate bond, and can be used without catalyst, high temperature, illumination or specific pH. Under the conditions, the synthesis and dynamic reversibility of the dynamic covalent polymer can improve the preparation efficiency, reduce the limitation of the use environment, and expand the application range of the polymer. In addition, by selectively controlling other conditions (such as adding auxiliaries, adjusting the reaction temperature, etc.), it is possible to accelerate or quench the dynamic covalent chemical equilibrium in a suitable environment in a desired state, which is now Some supramolecular chemistry and dynamic covalent systems are difficult to do.

(5) Dynamic covalent polymers can exhibit functional properties. By adjusting the dynamic components in the dynamic covalent polymer, the polymer can exhibit stimuli responsiveness and dilatancy. The polymer can respond to external stimuli such as external force, temperature, pH, light, etc., and change its state. The dynamically reversible inorganic boronic acid silicate bond and the supramolecular hydrogen bond can be re-bonded by changing the external conditions after the fracture, so that the material has plasticity, self-repairing and other functional properties, prolonging the service life of the carbon-containing chain polymer. At the same time, it also enables it to be applied to certain special fields.

detailed description

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

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

In another embodiment of the present invention, there is provided a dynamic covalent polymer comprising a BO-Si dynamic covalent bond, wherein any one of the B atoms is linked to three -O-, and wherein The linker to which any of the two different BO-Si dynamic covalent bonds are attached is a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.

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

The linking group L described in each embodiment of the present invention may be a linking group containing a carbon atom in a skeleton having a low molecular weight or a high molecular weight, preferably a polymer linking group having a molecular weight of more than 1000 Da, and more preferably a skeleton. The number of carbon atoms is not less than 20 and the molecular weight of the polymer is more than 1000 Da. The linker L skeleton further contains an optional hetero atom and/or an element atom which can form an elemental organic group, wherein the hetero atom optionally contained may be any suitable hetero atom, including but not limited to O, N. And S; optionally containing element atoms may be any suitable elemental atoms including, but not limited to, P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir. It is preferred that the linking group L is directly bonded to the Si atom of the B-O-Si bond through a carbon atom, and both the dynamics of the B-O-Si bond and the performance of the carbon atom-containing linking group L can be utilized to the utmost. The linker L can 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-type, comb, dendritic, hyperbranched), two-dimensional and three-dimensional clusters, and any suitable combination of the above structures, even particles having ordinary covalent cross-linking (including fibers and flake particles). 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 may be imparted with better rigidity and modulus; If it is lower than room temperature, it can impart better flexibility, elongation and plasticity to the dynamic copolymer. 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 polythiourethane 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 polyphenylsulfone group, but the present invention is not only Limited to this. According to an embodiment of the 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 performance of the linking group L can be exhibited, such as a wide range of optional glass transition temperatures, mechanical properties, chemical properties, optical properties, printing properties, and the like. It is preferred that the ratio of the sum of carbon atoms and hetero atoms in the dynamic covalent polymer skeleton in the linking group L to all atoms on the dynamic covalent polymer skeleton is not less than 50 mol%, more preferably not less than 80 mol%. The higher the proportion of carbon atoms and heteroatoms, the better the performance of the carbon-containing linker L.

In the present invention, in addition to the linking group L, the linking group may be any other suitable linking group, including but not limited to an element linking group, a hetero element linking group; wherein the element linking group refers to the linking group skeleton Elemental atomic composition, heterojunctional linker means that the linker backbone consists of heteroatoms and elemental atoms. Other linkers are preferably (poly)siloxanes, including crosslinked silica, most preferably polysiloxanes; the other linkers may also have any suitable topology, and one dynamic covalent polymer may contain different Other linkers.

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

The term "polymerization" reaction as used in the present invention is a growth process/action of a chain, including a process of synthesizing a product having a higher molecular weight by a reaction form such as polycondensation, polyaddition, ring-opening polymerization or the like. Among them, the reactants are generally compounds such as monomers, oligomers, and prepolymers which have a polymerization ability (that is, can be polymerized spontaneously or can be polymerized by an initiator or an external energy). The product obtained by polymerization of one reactant is referred to as a homopolymer. A product obtained by polymerization of two or more reactants is referred to as a copolymer. It should be noted that the "polymerization" described in the present invention includes a linear growth process of a reactant molecular chain, a branching process including a reactant molecular chain, a ring-forming process including a reactant molecular chain, and a reaction. The cross-linking process of molecular chains.

The term "crosslinking" reaction as used in the present invention primarily refers to the formation of two-dimensional, three-dimensional clusters by chemical and/or hydrogen bonding supramolecular chemical linkages between the reactant molecules and/or within the reactant molecules by covalent bonds. The process of forming a three-dimensional infinite network structure product is further formed. In the cross-linking process, the polymer chains generally grow in the two-dimensional/three-dimensional direction, gradually forming clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite networks. Unless specifically stated, cross-linking in the present invention refers to a three-dimensional infinite network structure above the gel point, including non-crosslinking including linear, branched, cyclic, two-dimensional clusters and gel points. A structure below the gel point such as a three-dimensional cluster structure.

The "gel point" described in the present invention means that the viscosity of the reactants suddenly increases during the crosslinking process, and gelation occurs, and the reaction point when a first three-dimensional network is reached, which is also called percolation. Threshold. a crosslinked product above the gel point having a three-dimensional infinite network structure, the crosslinked network forming a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose link structure, and A three-dimensional infinite network structure is not formed, and only a small number of three-dimensional network structures exist locally, and it does not belong to a cross-linked network that can form a whole across the entire polymer structure.

The "ordinary covalent bond" as used in the present invention refers to a covalent bond other than a dynamic covalent bond in the conventional sense, at a usual temperature (generally not higher than 100 ° C) and a usual time (generally Less than 1 day) is less difficult to break, including but not limited to common carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds. , hydrogen-oxygen bond, nitrogen-nitrogen bond, and the like.

The "dynamic covalent bond" as used in the embodiment of the present invention refers to an inorganic boronic acid borate bond (B-O-Si) and an optional inorganic boron boron bond (B-O-B). It should be noted that in the embodiment of the present invention, the inorganic boron oxyboron bond can be adjusted and controlled according to the selection of the reaction materials and the formulation ratio.

In the present invention, the dynamic covalent polymer contained in the dynamic covalent polymer may have one or more of any suitable polymer chain topology including, but not limited to, linear, cyclic (including But not limited to single-ring, multi-ring, nested ring, bridge ring), branching (including but not limited to star, H-shaped, comb, dendritic, hyperbranched), 2D/3D cluster, 3D infinite network Crosslinked structure and combinations of the above. The polymer chain may have pendant groups, side chains, and branches, and the side groups, side chains, and branches may continue to have pendant groups, side chains, and branches, that is, may have a multistage structure.

In the present invention, the dynamic covalent polymer and the cross-linking network in the composition thereof are all dynamic covalent cross-linking networks, and once the dynamic covalent cross-linking dissociates, the cross-linked structure is dissociated. However, particles having ordinary covalent cross-linking (including fibers and flake particles) present in a filled form are not excluded. The dynamic covalent crosslinking is also a crosslinking achieved by an inorganic boron silicate bond (B-O-Si) and an optional inorganic boron boron bond (B-O-B). In embodiments of the invention, the dynamic covalent bond may also be present in the non-crosslinked polymer/small molecule. Thus, the dynamic covalent polymer can be a dynamically covalently crosslinked polymer or a non-dynamic covalently crosslinked polymer.

In the present invention, the inorganic boron boron boron bond is less dynamic than the inorganic boronic acid silicate bond. Dynamically tunable dynamic covalent polymers can be obtained by adjusting and controlling the amount and proportion of inorganic boron boron boron bonds.

In an embodiment of the invention, the dynamic covalent bond may be present on the side chain and/or side of the backbone in addition to the polymer backbone backbone to form a dynamic covalent polymerization/crosslinking. Chains and/or branches and/or branched chains and their lower and/or lower multistage side groups and/or side chains and/or branches and/or branched chains. The invention also does not exclude the simultaneous inclusion of dynamic covalent bonds on the pendant and/or end groups of the polymer chain. Only dynamic covalent bonds on the backbone of the crosslinked network can constitute dynamic covalent crosslinks. Under suitable conditions, dynamic covalent bonds at any position in the dynamic covalent polymer can participate in dynamic reversible exchange. In the crosslinked network structure of the dynamic covalent polymer, once the dynamic covalent bond constituting the dynamic covalent crosslink is dissociated, the total effective crosslink degree of the polymer system will decrease. The number of inorganic boronic acid silicate bonds (the ratio of all bonds) on the skeleton between any two nearest crosslinking points containing inorganic boronic acid silicate bonds is not limited and may be one or more, preferably only one. When there is only one, the dynamic covalent polymer structure is more regular and the dynamics are more controllable.

The dynamic covalent polymer and its composition described in the present invention may optionally further comprise supramolecular hydrogen bonding, wherein the supramolecular hydrogen bonding may be intrachain/intramolecular non-crosslinking (intrachain/ Intramolecular ring formation) and/or interchain/intermolecular crosslinking and/or interchain/intermolecular non-crosslinking (polymerization). In an embodiment of the invention, the optionally containing supramolecular hydrogen bonding is carried out by a polymer backbone, pendant groups, side chains, branches, or any of the suitable components present in the dynamic covalent polymer. A hydrogen bond is formed between hydrogen bond groups at any one or more of the terminal groups. Wherein, the hydrogen bond group may also be present in the small molecule and/or the filler. In an embodiment of the invention, the hydrogen bond group is preferably present on the polymer chain containing the B-O-Si bond, which facilitates synergistic interaction between the dynamic covalent bond and the hydrogen bond.

In an embodiment of the invention, the dynamic covalent polymer composition may comprise one or more polymers; when a crosslinked network is present, it may be composed of one or more crosslinked networks, or may contain non-crosslinking at the same time. Polymer composition. When the dynamic covalent polymer is composed of two or more crosslinked networks, it may be composed of two or more crosslinked networks which are mutually blended, or may be composed of two or more interpenetrating crosslinked networks. It may also be constituted by a crosslinked network in which two or more portions are interpenetrated 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 contains both crosslinked and non-crosslinked components, the non-crosslinked components may be uniformly blended/interspersed in the crosslinked network, or may be unevenly dispersed in the crosslinked network; multiple non-crosslinking The ingredients can be blended uniformly or incompatible.

For the dynamic covalent polymer of the present invention, when the dynamic covalent crosslinking reaches above the gel point of the dynamic covalent crosslinking in at least one crosslinked network, it is ensured that even in the case of only one crosslinked network, The polymer may have a crosslinked structure under specific conditions.

In the present invention, the "skeleton" refers to the chain length direction of the polymer; for the crosslinked polymer, the "backbone" refers to any chain existing in the skeleton of the crosslinked network. Segments, which include the backbone and crosslinks on an infinite three-dimensional network backbone; for non-crosslinked polymers, the "backbone", unless otherwise specified, generally refers to the chain with the most links. Wherein, the "side chain" refers to a chain structure which is connected to the main chain skeleton of the polymer and distributed on the side of the main chain skeleton; wherein the "branched" / "bifurcation chain" may be The side chain can also be other chain structures that branch off from any chain. Herein, the "side group" refers to a chemical group which is linked to the polymer chain skeleton and distributed on the side of the chain skeleton. For "side chains", "branched chains" and "side groups", it may have a multi-stage structure, ie the side chains/branches may continue to have side groups and side chains/branches, side chains/branched sides Chains/branches can continue to have side groups and side chains/branches. Wherein, the term "end group" refers to a chemical group attached to an arbitrary chain of the polymer and located at the end of the chain. For hyperbranched and dendritic chains and their associated branched chain structures, the branch can also be regarded as the main chain, but in the present invention, the outermost chain is regarded as a branch, and the other chain is regarded as a main chain.

For the sake of simplicity of the description, in the specification of the present invention, the term "and/or" is used to mean that the term may include an option selected from the conjunction "and/or" or may be selected from the conjunction " And/or the options described hereinafter, or both 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 Saturation, temperature responsiveness, stress/strain responsiveness, especially dilatancy. When the dynamic covalent polymer is a non-crosslinked structure, the system will still be in a viscous flow state even if it undergoes dilatant flow under stress/strain, and does not generate an elastic state, which is advantageous for completely passing the viscosity. Flow loss mechanical energy. When the dynamic covalent polymer is a dynamic crosslinked structure, the viscous-elastic transition or the elastic reinforcement occurs when the system expands, and the viscous loss of the external force can be generated while the damage of the external force is reduced. Both situations have their own characteristics and advantages. Dynamic-related self-healing and temperature responsiveness facilitate self-repair, shape and recovery of dynamic covalent polymers, increase the safety of materials, extend the service life of materials, and improve the processability of materials.

In an embodiment of the invention, the dynamic covalent polymer may have one or more glass transition temperatures or may have no glass transition temperature. For the glass transition temperature of the dynamic covalent polymer, at least one of which is lower than 0 ° C, or between 0-25 ° C, or between 25-100 ° C, or higher than 100 ° C; The dynamic covalent polymer with a transformation temperature lower than 0 °C has better low-temperature performance, and is convenient to be used as a sealant, an elastomer, a gel, etc.; the dynamic covalent value of the glass transition temperature between 0-25 ° C The polymer can be used at room temperature, and can be conveniently used as an elastomer, sealant, gel, foam and ordinary solids; a dynamic covalent polymer having a glass transition temperature between 25 and 100 ° C is convenient. Obtaining common solids, foams and gels at room temperature; dynamic covalent polymers with a glass transition temperature higher than 100 ° C, good dimensional stability, mechanical strength, temperature resistance, favorable for stress-bearing materials, high impact resistance Materials are used. For dynamic covalent polymers with a glass transition temperature below 25 ° C, it can exhibit excellent dynamics, self-healing, and recyclability; for dynamic covalent polymers with a glass transition temperature higher than 25 ° C, It can reflect good shape memory ability, stress carrying capacity and impact resistance; in addition, the presence of supramolecular hydrogen bonds can further regulate the glass transition temperature of dynamic covalent polymers, for dynamic covalent polymers. Dynamic, cross-linking, and mechanical strength are added. For the dynamic covalent polymer in the present invention, it is preferred that at least one glass transition temperature is not higher than 50 ° C, and further preferably at least one glass transition temperature is not higher than 25 ° C, and most preferably each glass transition temperature is not Above 25 ° C. Each system having a glass transition temperature of not higher than 25 ° C is particularly suitable for use as a self-healing material or an energy absorbing material because of its good flexibility and flowability/creep property at daily use temperatures. The glass transition temperature of the dynamic covalent polymer can be measured by a method for measuring the glass transition temperature which is common in the art, such as DSC and DMA.

In an embodiment of the present invention, each raw material component of the dynamic covalent polymer may also have one or more glass transition temperatures, or may have no glass transition temperature, and its glass transition temperature is at least one lower than zero. °C, or between 0-25 ° C, or between 25-100 ° C, or higher than 100 ° C, wherein the material of the glass transition temperature below 0 ° C is convenient for low temperature in the preparation of dynamic covalent polymers Preparation and processing; the material of the compound having a glass transition temperature between 0 and 25 ° C can be prepared and processed at room temperature; the compound material having a glass transition temperature of between 25 and 100 ° C can be formed by using a conventional heating device. The manufacturing cost is low; the compound raw material having a glass transition temperature higher than 100 ° C can be used for preparing a high temperature resistant material having good dimensional stability and excellent mechanical properties. By using a variety of compound raw materials with different glass transition temperatures to prepare dynamic covalent polymers, dynamic covalent polymers with different glass transition temperatures can be obtained in different ranges, which can exhibit multiple comprehensive properties and dynamics. Sex and stability.

In an embodiment of the invention, the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.

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

The inorganic boron compound is selected from the group consisting of, but not limited to, boric acid, boric acid esters, borate salts, boric anhydrides, and boron halides. The boric acid may be orthoboric acid, metaboric acid or tetraboric acid. Borate esters include alkyl and allyl borate/triorgano borate hydrolyzed to boric acid in the presence of water, such as trimethyl borate, triethyl borate, triphenyl borate, 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-tolyldibutyl orthoborate, tris(2-methoxyethyl)borate, benzyldihydroborate Ester, diphenylhydroborate, isopropanol pinacol borate, triethanolamine borate, and the like. Suitable boronic acid anhydride includes, in addition to the formula B ₂ O ₃ is typically boron oxide, also including but not limited trialkoxy boroxine and derivatives thereof, e.g. trimethoxy boroxine, tris isopropoxide Alkyl boroxane, 2,2'-oxybis[4,4,6-trimethyl-1,3,2-dioxaboroxane, and the like. Suitable borate salts include, but are not limited to, diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, zinc metaborate, tripotassium borate, original Iron borate. 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 boron oxide of the formula B ₂ O ₃ [CAS Registry Number #1303-86-2] or boric acid of the general formula H ₃ BO ₃ [CAS Registry Number #10043-35-3]. As an example, the chemical structural formula of a suitable inorganic boron compound is as follows, but the invention is not limited thereto:

The silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal group and/or the pendant group of the compound contains a silyl group and/or a silanol precursor group. In the present invention, at least a part of the silicon-containing compound must contain the above-mentioned linking group L or the linking group L can be produced by a suitable reaction. Preferably, the silicon-containing compound contains only one silicon atom in each of the terminal groups and/or pendant groups of the silyl hydroxyl group and/or the silyl hydroxyl precursor group. Since the linker L skeleton contains carbon atoms, especially carbon-containing polymer linkers, a dynamic covalent polymer skeleton having rich structure and various properties can be obtained, and in particular, the presence of the skeleton carbon can be conveniently obtained with higher mechanical properties and can be printed. Sexual dynamic covalent polymers also facilitate the introduction of hydrogen bonding for additional dynamics. In addition to the above-described silicon-containing compound containing a linking group L, the other silicon-containing compound used to form a BO-Si bond may be selected from any suitable small molecule or macromolecular silicon-containing compound, preferably a polysiloxane, which may be organic or Inorganic silicone compounds, including silica.

The silanol group in the present invention refers to a structural unit (Si-OH) composed of a silicon atom and a hydroxyl group connected to the silicon atom, wherein the silanol group may be a silanol group (ie, a silyl group) The silicon atom is connected to at least one carbon atom through a silicon carbon bond, and at least one organic group is bonded to the silicon atom through the silicon carbon bond, or may be an inorganic silicon hydroxy group (ie, the silicon atom in the silicon hydroxy group is not Attached to the organic group), preferably a silicone hydroxyl group. In the present invention, one hydroxyl group (-OH) in the silanol group is a functional group.

The silanol precursor as described in the present invention refers to a structural unit (Si-Z) composed of a silicon atom and a group capable of hydrolyzing a hydroxyl group connected to the silicon atom, wherein Z is Hydrolyzed to give a hydroxyl group, which may be selected from the group consisting of halogen, cyano, oxocyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketone oxime Base, alkoxide group, and the like. Suitable silanol precursors are, for example, Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO ₄ CH ₃ , Si-OB(OCH ₃ ) ₂ , Si-NH ₂ , Si-N ( CH ₃ ) ₂ , Si-OCH ₃ , Si-COCH ₃ , Si-OCOCH ₃ , Si-CONH ₂ , Si-ON=C(CH ₃ ) ₂ , Si-ONa. In the present invention, one of the silyl hydroxyl precursors which can be hydrolyzed to give a hydroxyl group (-Z) is a functional group.

In order to explain the silicon-containing compound containing a linking group L in the present invention and the silicon-containing compound containing the linking group L, the following may be exemplified, but the present invention is not limited thereto.

Where m, n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.

In the present invention, any suitable inorganic boron compound and a compound containing a silicon hydroxy group and/or a silanol precursor may be used to form an inorganic boronic acid silicate bond, preferably an inorganic boric acid and a silanol group-containing macromolecular compound, inorganic boric acid. A macromolecular compound containing a silicon-containing hydroxy precursor, an inorganic borate (salt) and a silanol-containing macromolecular compound to form an inorganic boronic acid silicate bond, more preferably an inorganic boronic acid and a silicon-containing hydroxyl group-containing macromolecular compound, inorganic boron The acid ester and the silanol-containing macromolecular compound form an inorganic boronic acid silicate bond, and it is more preferred to use an inorganic boronic acid ester and a silicon-containing hydroxyl group-containing macromolecular compound to form an inorganic boronic acid silicate bond.

In an embodiment of the invention, the inorganic boron oxyboron bond may be formed in any suitable manner, preferably by dehydration of inorganic boric acid, deamination of inorganic boric acid with an inorganic boric acid organic ester.

In an embodiment of the present invention, the dynamic covalent polymer may be formed by forming an inorganic boronic acid silicate bond and an optional inorganic boron oxyboron bond, or may be prepared by first containing the inorganic boronic silicate bond and An optional boron boron bond compound is repolymerized/crosslinked to form the dynamic covalent polymer. In the present invention, based on the polyvalentity of Si atoms, a Si atom participating in the formation of B-O-Si on a silicon-containing compound containing a linking group L and other linking groups may form up to three B-O-Sis, which share one Si atom. Moreover, since the boron atom is a trivalent structure, once the raw material component has a suitable reactive group, the polymerization process to form the inorganic boronic acid silicate and the inorganic boron oxyboron bond can easily cause bifurcation and can be further crosslinked.

In the embodiment of the present invention, the number of teeth is not limited for the optional supramolecular hydrogen bond. The number of teeth is a number of hydrogen bonds composed of a hydrogen bond donor (D, that is, a hydrogen atom) of a hydrogen bond group and a hydrogen bond acceptor (A, that is, an electronegative atom accepting a hydrogen atom), each DA The combination is a tooth (as shown in the following formula, the hydrogen bond bonding of the one, two and three tooth hydrogen bond groups is respectively shown).

If the number of teeth of the hydrogen bond is large, the strength is large, and the dynamics of the hydrogen bond is weak, which can function to improve the mechanical properties (modulus and strength) of the dynamic covalent polymer. If the number of teeth of the hydrogen bond is small, the strength is low, the dynamics of hydrogen bonding is strong, and dynamic properties such as self-healing property, energy absorption property, etc. can be provided together with the dynamic covalent inorganic silicon silicate bond and the inorganic boron oxyboron bond. . In an embodiment of the invention, preferably no more than four teeth hydrogen bonding, more preferably hydrogen bonding groups participating in the formation of no more than four teeth by hydrogen bonding groups on the side groups and/or side chains.

In an embodiment of the present invention, the hydrogen bond group may be a hydrogen bond group having both a hydrogen bond acceptor and a hydrogen bond donor; or a part of the hydrogen bond group may have a hydrogen bond donor, and the other part The hydrogen bonding group contains a hydrogen bond acceptor; preferably, both the acceptor and the donor are contained.

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

Wherein A is selected from the group consisting of an oxygen atom and a sulfur atom; D is selected from a nitrogen atom and a CR group; and X is a halogen atom;

Indicates a linkage to a polymer chain, a cross-linking link, or any other suitable group, including a hydrogen atom. Wherein R is selected from a hydrogen atom, a substituted atom, and a substituent.

When it is a substituent, the number of carbon atoms of R is not particularly limited, but the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 10.

As the substituent, the structure of R is not particularly limited and includes, but is not limited to, a linear structure, a branched structure containing a side group, or a cyclic structure. 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 is preferably an aliphatic ring.

When it is a substituent, R may contain a hetero atom, and may contain a hetero atom.

R may be selected from a hydrogen atom, a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 heteroalkyl group, a substituted C _1-20 hydrocarbon group or a substituted heterohydrocarbyl group. Here, the substituted atom or the substituent in R is not particularly limited, and is any one selected from the group consisting of a halogen atom, a hydrocarbon group substituent, and a hetero atom-containing substituent.

More preferably, R is a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 alkenyl group, an aryl group, an aromatic hydrocarbon group, a C _1-20 aliphatic hydrocarbon group, a heteroaryl group, a heteroaryl hydrocarbon group, and a C _1-20 group. Any atom or group of an alkoxyacyl group, an aryloxyacyl group, a C _1-20 alkylthio acyl group, an arylthio acyl group, or a substituted form of any one of the groups.

Specifically, R may be selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Indenyl, fluorenyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl , eicosyl, allyl, propenyl, vinyl, phenyl, methylphenyl, butylphenyl, benzyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxy Carbonyl, methylthiocarbonyl, ethylthiocarbonyl, phenylthiocarbonyl, benzylthiocarbonyl, ethylaminocarbonyl, benzylaminocarbonyl, methoxythiocarbonyl, ethoxythiocarbonyl, phenoxythiocarbonyl , benzyloxythiocarbonyl, methylthiocarbonylcarbonyl, ethylthiothiocarbonyl, phenylthiothiocarbonyl, benzylthiothiocarbonyl, ethylaminothiocarbonyl, benzylaminothiocarbonyl, substituted C _1-20 alkyl, substituted C _1-20 alkenyl, substituted aryl, substituted arene, substituted C _1-20 aliphatic, substituted heteroaryl, substituted heteroaryl Substituted C _1-20 alkoxycarbonyl, substituted aryloxycarbonyl, substituted C _1-20 alkylthiocarbonyl, substituted arylthiocarbonyl substituted C _1-20 alkoxythio Any atom or group of a carbonyl group, a substituted aryloxythiocarbonyl group, a substituted C _1-20 alkylthiothiocarbonyl group, a substituted arylthiothiocarbonyl group, or the like. Wherein, when the structure involved has an isomer, if it is not specifically specified, it may be any one of them, for example, for an alkyl group, if it is not specifically specified, it means that any position is lost. Hydrocarbyl groups formed by hydrogen atoms, specifically such as butyl include, but are not limited to, n-butyl, t-butyl; octyl includes, but is not limited to, n-octyl, 2-ethylhexyl. Wherein the substituted atom or the substituent is selected from any one of a halogen atom, a hydrocarbon group substituent, and a hetero atom-containing substituent.

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

among them,

Indicates a linkage to a polymer chain, a cross-linking link, or any other suitable group, including a hydrogen atom.

The structures represented by the general formulae (1) and (2) may be a side group, an end group, a chain structure or the like, or may form a cyclic structure. The ring structure may be a single ring structure, a polycyclic structure, a spiro ring structure, a fused ring structure, a bridge ring structure, a nested ring structure, or the like.

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

In an embodiment of the invention, the hydrogen bond group more preferably contains at least one of the following structural components:

among them,

Indicates a linkage to a polymer chain, a cross-linking link, or any other suitable group, including a hydrogen atom. In an embodiment of the invention, the hydrogen bond group is preferably an amide group, a carbamate group, a urea group, a thiourethane group, a silyl carbamate group or a derivative of the above groups.

The backbone hydrogen bond group on a suitable chain backbone is for example (but the invention is not limited to this):

Suitable pendant hydrogen bonding groups and terminal hydrogen bonding groups are for example (but the invention is not limited to this):

Wherein m and n are the number of repeating units, and may be a fixed value or an average value, preferably less than 20, more preferably less than 5.

In an embodiment of the present invention, the hydrogen bonding group forming a hydrogen bond may be a complementary combination between different hydrogen bonding groups, or a self-complementary combination between the same hydrogen bonding groups, as long as the group It is sufficient to form a suitable hydrogen bond. Some combinations of hydrogen bonding groups can be exemplified as follows, but the present invention is not limited to this:

In the present invention, the same compound/polymer may contain one or more hydrogen bonding groups, and the same crosslinking network may also contain one or more hydrogen bonding groups, that is, dynamic The covalent polymer may contain a combination of one or more hydrogen bonding groups. The hydrogen bond group may be at any one or more of the main chain, the side group, the side chain, the branch of the linker L, or the main chain, the side group, the side chain, and the branch of the other linker. Any one or more places. The hydrogen bond group may be formed by any suitable chemical reaction, for example, by a 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; by an isocyanate The reaction between the group and the hydroxyl group, the thiol group, and the carboxyl group is formed; it is formed by a reaction between a succinimide ester group and an amino group, a hydroxyl group, or a thiol group.

In the present invention, the content of the hydrogen bond group and its hydrogen bonding is not limited. The supramolecular hydrogen bonding may be formed during the formation of the polymer component in the dynamic covalent polymer; or may be a polymer component formed by pre-forming a supramolecular hydrogen bond to form a dynamic covalent polymer; Supramolecular hydrogen bonding can be produced during the subsequent molding of the dynamic covalent polymer, but the invention is not limited thereto.

In the present invention, there may be other various embodiments, and any one of the embodiments may optionally contain the inorganic boron boron boron bond and/or hydrogen bonding, and those skilled in the art may according to the present invention. The logic and context are implemented reasonably and effectively.

The present invention also provides a method of absorbing energy, characterized in that a dynamic covalent polymer is provided and energy is absorbed as an energy absorbing material, wherein the dynamic covalent polymer contains BO-Si dynamic covalent a bond in which any one of the B atoms is bonded to three -O-, and wherein the linking group which is bonded to at least two different Si atoms in the BO-Si dynamic covalent bond based on different B atoms contains a linking group L, The linker L described contains a carbon atom on the backbone of the dynamic covalent polymer chain.

In the present invention, the raw material component for preparing the dynamic covalent polymer includes, in addition to the inorganic boron compound and the silicon-containing compound described above, other polymers, auxiliaries, and fillers which can be added/used. The addenda/available material together with the reaction product of the inorganic boron compound and the silicon-containing compound constitutes the dynamic covalent polymer composition by blending.

In an embodiment of the invention, the dynamic covalent polymer or a composition thereof may be in the form of a solution, an emulsion, a paste, a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer). a swelling gel, a plasticizer swelling gel, an ionic liquid swelling gel, a foam, etc., wherein the content of the small molecular weight component contained in the ordinary solid and the foam is generally not more than 10% by weight, and the small molecular weight component contained in the gel The content is generally not less than 50% by weight. Among them, the dynamic polymer ordinary solid has a fixed shape and volume, high strength and high density, and is suitable for high-strength explosion-proof wall or instrument casing; the elastic body has the general property of ordinary solid, but the elasticity is better and the softness is more High, more suitable as energy absorbing material such as damping/damping; dynamic polymer gel is soft in texture, has good energy absorption and elasticity, and is suitable for preparing high damping energy absorbing materials; dynamic polymer foam material has density The soft foam material also has good elasticity and energy absorbing properties when it is low in weight, light in weight, and high in specific strength.

In an embodiment of the invention, the dynamic covalent polymer gel is preferably obtained by dynamic crosslinking in a swelling agent, including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof. It 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 implement the logic and the context of the present invention reasonably and effectively.

In the preparation process of the dynamic covalent polymer foaming material, the dynamic covalent polymer is mainly foamed by the mechanical foaming method, the physical foaming method and the chemical foaming method.

Wherein, the mechanical foaming method is to introduce a large amount of air or other gas into the emulsion, suspension or solution of the polymer into a uniform foam by vigorous stirring during the preparation of the dynamic covalent polymer, and then It is gelled and solidified by physical or chemical changes to become a foam. To shorten the molding cycle, air can be introduced and an emulsifier or surfactant can be added.

Wherein, the physical foaming method utilizes physical principles to achieve foaming of the polymer in the preparation process of the dynamic covalent polymer, and generally includes the following four methods: (1) inert gas foaming method, that is, Pressurizing the inert gas into the molten polymer or the paste material under pressure, and then heating the pressure under reduced pressure to expand and foam the dissolved gas; (2) evaporating the gasification foam by using a low-boiling liquid, that is, lowering the boiling point The liquid is pressed into the polymer or under a certain pressure and temperature condition, the liquid is dissolved into the polymer particles, and then the polymer is heated and softened, and the liquid is vaporized by evaporation to foam; (3) dissolution method, that is, The liquid medium is immersed in the polymer to dissolve the solid substance added in advance, so that a large amount of pores appear in the polymer to be foamed, for example, the soluble substance salt, starch, etc. are first mixed with the polymer, and then formed into a product, and then The product is repeatedly treated in water to dissolve the soluble matter to obtain an open-cell foam product; (4) a hollow microsphere method, that is, a hollow microsphere is added to the plastic and then solidified to form a closed-cell foam; The method is preferably used dissolved in an inert gas and low boiling liquid foaming in the polymer. The physical foaming method has the advantages of less toxicity in operation, lower cost of foaming raw materials, and no residual body of foaming agent. In addition, it can also be prepared by freeze drying.

Wherein, the chemical foaming method is a method of foaming along with a chemical reaction in a foaming process of a dynamic covalent polymer, which generally comprises the following two methods: (1) thermal decomposition foaming The agent foaming method is a method in which a gas liberated by heating with a chemical foaming agent is used for foaming. (2) A foaming method in which a polymer component interacts to generate a gas, that is, a chemical reaction occurring between two or more components in a foaming system to generate an inert gas such as carbon dioxide or nitrogen to cause a polymer Expand and foam. In order to control the balance between the polymerization reaction and the foaming reaction during the foaming process, in order to ensure a good quality of the product, a small amount of a catalyst and a foam stabilizer (or a surfactant) are generally added. Among them, it is preferred to carry out foaming by a method of adding a chemical foaming agent to the polymer.

In the preparation of the dynamic covalent polymer, the dynamic covalent polymer foam material is preferably molded by three methods of compression foam molding, injection foam molding, and extrusion foam molding.

Among them, the molding foam molding, the process is relatively simple and easy to control, and can be divided into one-step method and two-step method. One-step molding means that the mixed material is directly put into the cavity for foam molding; the two-step method refers to pre-expansion treatment of the mixed material, and then into the cavity for foam molding. Among them, since the one-step molding foam molding is more convenient to operate than the two-step method and the production efficiency is high, it is preferable to carry out the compression foam molding by the one-step method.

Wherein, the injection foam molding process and equipment are similar to ordinary injection molding, and the bubble nucleation stage is heated and rubbed to make the material into a melt state after the material is added to the screw, and the foaming agent is passed. The control of the metering valve is injected into the material melt at a certain flow rate, and then the foaming agent is uniformly mixed through the mixing elements of the screw head to form a bubble core under the action of the nucleating agent. Both the expansion stage and the solidification setting stage occur after the end of the filling cavity. When the cavity pressure drops, the expansion process of the bubble core occurs, and the bubble body solidifies and sets as the mold cools down.

Wherein, the extrusion foam molding, the process and equipment are similar to ordinary extrusion molding, the foaming agent is added to the extruder before or during the extrusion process, and the melt flows through the pressure at the head. Upon falling, the blowing agent volatilizes to form the desired foamed structure. Because it can not only achieve continuous production, but also is more competitive in cost than injection foam molding, it is currently the most widely used foam molding technology.

In the preparation of the dynamic covalent polymer, those skilled in the art can select a suitable foaming method and a foam molding method to prepare the dynamic covalent polymer foam according to the actual preparation conditions and the target polymer properties.

In an embodiment of the invention, the structure of the dynamic covalent polymer foam material involves three types of open-cell structures, closed-cell structures, and half-open half-close structures. In the open-cell structure, the cells and the cells are connected to each other or completely connected, and the single or three-dimensional can pass through a gas or a liquid, and the bubble diameter ranges from 0.01 to 3 mm. The closed-cell structure has an independent cell structure, and the inner cell is separated from the cell by a wall membrane, and most of them are not connected to each other, and the bubble diameter is 0.01-3 mm. The cells contained in the cells are connected to each other and have a semi-open structure. For the foam structure which has formed a closed cell, it can also be made into an open-cell structure by mechanical pressure or chemical method, and those skilled in the art can select according to actual needs.

In the embodiment of the present invention, the dynamic covalent polymer foam material can be classified into soft, hard and semi-rigid according to its hardness classification: (1) soft foam at 23 ° C and 50% relative. The modulus of elasticity of the foam is less than 70 MPa under humidity; (2) the rigid foam has a modulus of elasticity greater than 700 MPa at 23 ° C and 50% relative humidity; (3) a semi-rigid (or semi-soft) foam, The foam between the above two types has a modulus of elasticity between 70 MPa and 700 MPa.

In an embodiment of the present invention, the dynamic covalent polymer foam material can be further classified into low foaming, medium foaming, and high foaming according to its density. a low foaming foam material having a density of more than 0.4 g/cm ³ and a foaming ratio of less than 1.5; a medium foamed foam material having a density of 0.1 to 0.4 g/cm ³ and a foaming ratio of 1.5 to 9; A foamed foam having a density of less than 0.1 g/cm ³ and a foaming ratio of greater than 9.

In other embodiments of the present invention, the other polymers, auxiliaries, and fillers that may be added/used may be any suitable materials.

Among them, the other polymers described can be used as additives in the system to improve material properties, impart new properties to materials, improve material use and economic benefits, and achieve comprehensive utilization of materials. Other polymers which may be added/used may be selected from natural polymer compounds, synthetic resins, synthetic rubbers, synthetic fibers. The present invention does not limit the properties of the added polymer and the molecular weight thereof, and may be an oligomer or a high polymer depending on the molecular weight, and may be a homopolymer or a copolymer depending on the polymerization form. In the specific use process, it should be selected according to the performance of the target material and the needs of the actual preparation process.

When the other polymer is selected from natural polymer compounds, it may be selected from any one or any of the following natural polymer compounds: natural rubber, chitosan, chitin, natural protein, and the like.

When the other polymer is selected from a synthetic resin, it may be selected from any one or any of the following synthetic resins: polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinyl chloride, poly Vinylidene chloride, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole, poly Ethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene, 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, ethylene-vinyl acetate copolymer, acrylonitrile- Acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, Ethylene - vinyl acetate copolymer, polyvinyl pyrrolidone, epoxy resin, phenol resin, urea resin, unsaturated polyester.

When the other polymer is selected from synthetic rubber, it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl Rubber, ethylene propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, urethane rubber, chloroether rubber, thermoplastic elastomer, etc.

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

In the preparation of the polymer material, the other polymers are preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polymethacrylic acid. Methyl ester, epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl rubber, ethylene propylene rubber, silicone rubber, urethane rubber, thermoplastic elastomer.

The additive that can be added/used can improve the material preparation process, improve product quality and yield, reduce product cost, or impart a unique application property to the product. The auxiliary agent is selected from any one or any of the following auxiliary agents: a synthetic auxiliary agent, including a catalyst, an initiator, a stabilizing auxiliary agent, including an antioxidant, a light stabilizer, a heat stabilizer; and an improvement of mechanical properties. Additives, including chain extenders, toughening agents, coupling agents; additives to improve processing properties, including lubricants, mold release agents; softening and lightening additives, including plasticizers, foaming agents, Dynamic modifiers; additives for changing surface properties, including antistatic agents, emulsifiers, dispersants; additives for changing shades, including colorants, fluorescent whitening agents, matting agents; flame retardant and smoke suppressing additives, including Flame retardant; other additives, including nucleating agents, rheological agents, thickeners, leveling agents.

The catalyst in the auxiliary agent is capable of accelerating the reaction rate of the reactants in the reaction process by changing the reaction pathway and reducing the activation energy of the reaction. In an embodiment of the present invention, the catalyst includes, but is not limited to: (1) a catalyst for polyurethane synthesis: an amine catalyst such as triethylamine, triethylenediamine, bis(dimethylaminoethyl)ether, 2-(2-Dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N-(dimethylaminopropyl) Diisopropanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisamine ethyl ether, tetramethyldipropylene triamine, N,N-dimethylcyclohexylamine ,N,N,N',N'-tetramethylalkylenediamine, N,N,N',N',N'-pentamethyldiethylenetriamine, N,N-dimethyl Ethanolamine, N-ethylmorpholine, 2,4,6-(dimethylaminomethyl)phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N,N-dimethylbenzylamine, N, N-dimethylhexadecylamine, etc.; organometallic catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctylate, lead isooctanoate, potassium oleate, zinc naphthenate , cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, and the like. (2) Catalyst for polyolefin synthesis: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, diethylaluminum chloride, titanium tetrachloride, titanium trichloride, trifluoro Boron ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, sesquiethylaluminum chloride, vanadium oxychloride, triisobutylene Aluminum, nickel naphthenate, rare earth naphthenic acid, and the like. (3) The CuAAC reaction is synergistically catalyzed by a monovalent copper compound and an amine ligand. The monovalent copper compound may be selected from a Cu(I) salt such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; or may be selected from a Cu(I) complex such as [Cu(CH ₃ CN) ₄ ]PF ₆ , [Cu(CH ₃ CN) ₄ ]OTf, CuBr(PPh ₃ ) _{3 ,} etc.; it can also be formed in situ from elemental copper and divalent copper compounds (such as CuSO ₄ , Cu(OAc) ₂ ); The (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 tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), tris[(1-tert-butyl-1H-1, 2,3-triazol-4-yl)methyl]amine (TTTA), tris(2-benzimidazolylmethyl)amine (TBIA), hydrated phenanthroline sodium disulfonate, etc.; among them, amine ligand TBTA and TTTA are preferred. (4) Thiol-ene reaction catalyst: photocatalyst, such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-2-phenylacetophenone, etc.; nucleophilic A reagent catalyst such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine or the like. The amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.

The initiator in the auxiliary agent, which can cause activation of the monomer molecule during the polymerization reaction to generate a radical, increase the reaction rate, and promote the reaction, including but not limited to any one or more of the following initiators: Organic peroxides such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate Ester, t-butyl peroxybenzoate, t-butyl peroxypivalate, di-tert-butyl peroxide, dicumyl hydroperoxide; azo compounds such as azobisisobutyronitrile AIBN), azobisisoheptanenitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, etc.; wherein the initiator is preferably lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, persulfuric acid Potassium. The amount of the initiator to be used is not particularly limited and is usually from 0.1 to 1% by weight.

The antioxidant in the auxiliary agent can delay the oxidation process of the polymer sample, ensure the material can be smoothly processed and prolong its service life, including but not limited to any one or any of the following antioxidants. : hindered phenols such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl)butane, tetra [ --(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol); sulfur-containing hindered Phenols such as 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert-butylphenol]; a triazine-based hindered phenol such as 1,3,5-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-s-triazine; a trimeric isocyanate hindered phenol, Such as tris(3,5-di-tert-butyl-4-hydroxybenzyl)-triisocyanate; amines such as N,N'-bis(β-naphthyl)p-phenylenediamine, N,N'-diphenyl P-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine; sulfur-containing, such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; Phosphates, such as triphenyl phosphite, phosphorous Trimethylphenyl ester, tris[2.4-di-tert-butylphenyl]phosphite, etc.; among them, the antioxidant is preferably tea polyphenol (TP), butylated hydroxyanisole (BHA), dibutylhydroxytoluene ( BHT), tert-butyl hydroquinone (TBHQ), tris[2.4-di-tert-butylphenyl]phosphite (antioxidant 168), tetra[β-(3,5-di-tert-butyl-4) -Hydroxyphenyl)propionic acid] pentaerythritol ester (antioxidant 1010). The amount of the antioxidant to be used is not particularly limited and is usually from 0.01 to 1% by weight.

The light stabilizer in the auxiliary agent can prevent photoaging of the polymer sample and prolong its service life, including but not limited to any one or any of the following light stabilizers: a light shielding agent 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-hydroxyl -4-n-butoxyphenyl)-1,3,5-s-triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; pioneering UV absorbers such as salicylic acid P-tert-butylphenyl ester, bisphenol A disalicylate; UV quencher, such as bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2,2' - thiobis(4-tertylphenoloxy) nickel; hindered amine light stabilizers such as bis(2,2,6,6-tetramethylpiperidine) sebacate, benzoic acid (2,2 6,6-tetramethylpiperidine), tris(1,2,2,6,6-pentamethylpiperidinyl)phosphite; other light stabilizers, such as 3,5-di-tert-butyl (2,4-di-tert-butylbenzene) -4-hydroxybenzoate, alkane Phosphoric acid amide, zinc N,N'-di-n-butyldithiocarbamate, nickel N,N'-di-n-butyldithiocarbamate, etc.; wherein the light stabilizer is preferably carbon black or sebacic acid bis ( 2,2,6,6-Tetramethylpiperidine) (light stabilizer 770). The amount of the photostabilizer to be used is not particularly limited and is generally from 0.01 to 0.5% by weight.

The heat stabilizer in the auxiliary agent can make the polymer sample not undergo chemical change due to heat during processing or use, or delay the change to achieve the purpose of prolonging the service life, including but not limited to any of the following Or any of several heat stabilizers: lead salts, such as tribasic lead sulfate, lead dibasic phosphite, lead dibasic stearate, lead dibasic lead, lead tribasic maleate , salt-based lead silicate, lead stearate, lead salicylate, lead dibasic phthalate lead, basic lead carbonate, silica gel coprecipitated lead silicate; metal soap: such as cadmium stearate, hard Barium citrate, calcium stearate, lead stearate, zinc stearate; organotin compounds such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di(n-butyl) maleate, double horse Acid monooctyl ester di-n-octyltin, di-octyl acetic acid iso-octyl di-n-octyl tin, Jingxi C-102, di-mercaptoacetic acid isooctyl dimethyl tin, dithiol dimethyl tin and its compound; Stabilizers, such as thiol sulfonium salts, thioglycol thiol oximes, fluorenyl carboxylic acid oximes, carboxylic acid esters oxime; epoxy Compounds such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites such as triaryl phosphite, trialkyl phosphite, triaryl phosphite, alkyl aromatic mixed esters, polymeric subtypes a phosphate; a polyhydric alcohol such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; wherein the heat stabilizer is preferably barium stearate, calcium stearate, di-n-butyltin dilaurate, Di(n-butyl)butyl maleate. The amount of the heat stabilizer to be used is not particularly limited and is usually from 0.1 to 0.5% by weight.

The chain extender in the auxiliary agent can react with a reactive group on the reactant molecular chain to expand the molecular chain and increase the molecular weight, including but not limited to any one or more of the following chain extenders. : Polyol chain extenders, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, p-benzene Diphenol dihydroxyethyl ether (HQEE), resorcinol bishydroxyethyl ether (HER), p-hydroxyethyl bisphenol A; polyamine chain extender, such as diaminotoluene, diaminoxylene, Tetramethylxylylenediamine, tetraethyldibenzylidenediamine, tetraisopropyldiphenylidenediamine, m-phenylenediamine, tris(dimethylaminomethyl)phenol, diamino Diphenylmethane, 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 3,5-dimethylthiotoluenediamine (DMTDA), 3,5-diethyl Toluene diamine (DETDA), 1,3,5-triethyl-2,6-diaminobenzene (TEMPDA); alcohol amine chain extenders, such as triethanolamine, triisopropanolamine, N, N'- Bis(2-hydroxypropyl)aniline. The amount of the chain extender to be used is not particularly limited and is usually from 1 to 20% by weight.

The toughening agent in the auxiliary agent can reduce the brittleness of the polymer sample, increase the toughness, and improve the load bearing strength of the material, including but not limited to any one or any of the following toughening agents: methyl methacrylate- Butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and modified product thereof, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer , ethylene propylene rubber, EPDM rubber, butadiene rubber, styrene 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), chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited and is usually from 5 to 10% by weight.

The coupling agent in the auxiliary agent can improve the interface property between the polymer sample and the inorganic filler or the reinforcing material, reduce the viscosity of the material melt during the plastic processing, and improve the dispersion of the filler to improve the processing performance, and further The article is provided with good surface quality and mechanical, thermal and electrical properties, including but not limited to any one or any of the following coupling agents: organic acid chromium complex, silane coupling agent, titanate coupling agent , a sulfonyl azide coupling agent, an aluminate coupling agent, etc.; wherein the coupling agent is preferably γ-aminopropyltriethoxysilane (silane coupling agent KH550), γ-(2,3-epoxy) Propoxy)propyltrimethoxysilane (silane coupling agent KH560). The amount of the coupling agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.

The lubricant in the auxiliary agent can improve the lubricity of the polymer sample, reduce friction and reduce interfacial adhesion performance, including but not limited to any one or any of the following lubricants: saturated hydrocarbons and halogenated hydrocarbons Such as solid paraffin, microcrystalline paraffin, liquid paraffin, 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 stearic acid amide or stearic acid amide, oleamide or oleic acid amide, erucamide, N, 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.; Preference is given to solid paraffin, liquid paraffin, stearic acid, low molecular weight polyethylene. The amount of the lubricant to be used is not particularly limited and is usually from 0.5 to 1% by weight.

The release agent in the auxiliary agent, which can make the polymer sample easy to demold, the surface is smooth and clean, including but not limited to any one or any of the following mold release agents: paraffin hydrocarbon, soap, two Methyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber, etc. Dimethicone, polyethylene glycol. The amount of the releasing agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.

a plasticizer in the additive capable of increasing the plasticity of the polymer sample, resulting in a decrease in hardness, modulus, softening temperature, and embrittlement temperature of the polymer, and an increase in elongation, flexibility, and flexibility. Including but not limited to any one or any of the following plasticizers: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, ortho-benzene Diheptyl formate, diisononyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate, butyl phthalate, dicyclohexyl phthalate , bis(tris) phthalate, di(2-ethyl)hexyl terephthalate; phosphates such as tricresyl phosphate, diphenyl-2-ethylhexyl phosphate; fatty acids Esters, such as di(2-ethyl)hexyl adipate, di(2-ethyl)hexyl sebacate; epoxy compounds such as epoxy glycerides, epoxidized fatty acid monoesters, rings Oxytetrahydrophthalate, epoxidized soybean oil, (2-ethylhexyl) epoxy stearate, 2-ethylhexyl epoxide, 4,5-epoxytetrahydroortho Diphenyl phthalate (2-B ) Hexyl boxwood acetyl methyl ricinoleate; diol lipids, such as C _{5 ~ 9} glycol acrylate, C _{5 ~ 9} triethylene glycol diethyl ester; chlorine-containing hydrocarbons, such as paraffins green , chloro fatty acid esters; polyesters, such as oxalic acid 1,2-propanediol polyester, azelaic acid 1,2-propanediol polyester, petroleum benzene sulfonate, trimellitate, citrate And dipentaerythritol ester, etc.; wherein the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), phthalic acid Diisodecyl ester (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited and is usually from 5 to 20% by weight.

The foaming agent in the auxiliary agent can foam the polymer sample into pores, thereby obtaining a lightweight, heat-insulating, sound-insulating, elastic polymer material, including but not limited to any one or more of the following Blowing agent: physical foaming agent, such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether , methyl chloride, dichloromethane, dichloroethylene, dichlorodifluoromethane, chlorotrifluoromethane; inorganic foaming agents, such as sodium bicarbonate, ammonium carbonate, ammonium hydrogencarbonate; organic foaming agents, such as N, N' -dinitropentamethylenetetramine, N,N'-dimethyl-N,N'-dinitroso-terephthalamide, azodicarbonamide, arsenazo hydride, azodi Diisopropyl carbonate, potassium azoformate, azobisisobutyronitrile, 4,4'-oxobisbenzenesulfonyl hydrazide, benzenesulfonyl hydrazide, tridecyltriazine, p-toluenesulfonyl semicarbazide , biphenyl-4,4'-disulfonyl azide; foaming accelerators such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, lead dibasic phosphite, stearic acid Lead acid, hard Cadmium citrate, zinc stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalene Phenol, aliphatic amine, amide, hydrazine, isocyanate, thiol, thiophenol, thiourea, sulfide, sulfone, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, and the like. Among them, the blowing agent is preferably sodium hydrogencarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N, N'-dinitropentamethyltetramine (foaming agent H), N, N' -Dimethyl-N,N'-dinitroso-terephthalamide (foaming agent NTA), physical microsphere foaming agent, and the amount of the foaming agent to be used are not particularly limited, and are generally 0.1 to 30% by weight. .

The dynamic modifier in the auxiliaries is capable of enhancing the dynamic polymer dynamics in order to obtain optimum desired properties, generally with free hydroxyl or free carboxyl groups, or compounds capable of giving or accepting electron pairs, These include, but are not limited to, water, sodium hydroxide, alcohols (including silanols), carboxylic acids, Lewis acids, Lewis bases, and the like. The amount of the dynamic regulator used is not particularly limited and is usually from 0.1 to 10% by weight.

The antistatic agent in the auxiliary agent can guide or eliminate the harmful charges accumulated in the polymer sample, so that it does not cause inconvenience or harm to production and life, including but not limited to any one or any of the following Electrostatic agent: anionic antistatic agent, such as alkyl sulfonate, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate diethanolamine salt, p-nonyldiphenyl ether sulfonate potassium, phosphate derivative, Phosphate, poly(ethylene oxide alkyl ether alcohol phosphate), phosphate derivative, fatty amine sulfonate, sodium butyrate sulfonate; cationic antistatic agent, such as fatty ammonium hydrochloride, lauryl triamide Ammonium chloride, lauryl trimethylamine bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agent, such as alkyl dicarboxymethyl ammonium ethyl salt, lauryl betaine , N,N,N-trialkylammonium acetyl (N'-alkyl)amine ethyl salt, N-lauryl-N,N-dipolyoxyethylene-N-ethylphosphonate, N-alkane Amino acid salt; nonionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, alkylphenol ethylene oxide adduct, Tripolyoxyethylene ether phosphate, glycerol mono-fatty acid ester; polymer antistatic agent, such as ethylene oxide propylene oxide adduct of ethylene diamine, polyallylamide N-quaternary ammonium salt substitute, Poly 4-vinyl-1-pyrimidinylphosphonic acid-p-butylphenyl ester salt or the like; wherein, the antistatic agent is preferably lauryl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P). The amount of the antistatic agent to be used is not particularly limited and is usually from 0.3 to 3% by weight.

The emulsifier in the auxiliary agent can improve the surface tension between various constituent phases in the polymer mixture containing the auxiliary agent to form a uniform and stable dispersion system or emulsion, which is preferably used for the emulsion. Polymerization/crosslinking, including but not limited to any one or any of the following emulsifiers: anionic, such as higher fatty acid salts, alkyl sulfonates, alkyl benzene sulfonates, sodium alkyl naphthalene sulfonates, Succinate sulfonate, petroleum sulfonate, fatty alcohol sulfate, castor oil sulfate, sulfated butyl ricinate, phosphate ester, fatty acyl-peptide condensate; cationic type, such as alkyl ammonium Salt, alkyl quaternary ammonium salt, alkyl pyridinium salt; zwitterionic type, such as carboxylate type, sulfonate type, sulfate type, phosphate type; nonionic type, such as fatty alcohol polyoxyethylene ether, alkyl Phenolic polyoxyethylene ether, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester , an alcohol amine fatty acid amide, etc.; wherein the emulsifier is preferably dodecylbenzene Sodium, sorbitan fatty acid esters, triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited and is usually from 1 to 5% by weight.

The dispersing agent in the auxiliary agent can disperse the solid floc cluster in the polymer mixture into fine particles and suspend in the liquid, uniformly disperse solid and liquid particles which are difficult to be dissolved in the liquid, and also prevent the particles from being Settling and coagulation to form a stable suspension, including but not limited to any one or any of the following dispersants: anionic, such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium petroleum sulfonate; cationic Nonionic type, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic type, such as silicate, condensed phosphate; wherein the dispersing agent is preferably sodium dodecyl benzene sulfonate, Naphthalene methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether. The amount of the dispersant to be used is not particularly limited and is usually from 0.3 to 0.8% by weight.

The coloring agent in the auxiliary agent can make the polymer product exhibit the desired color and increase the surface color, including but not limited to any one or any of the following coloring agents: inorganic pigments such as titanium white and chrome yellow. , cadmium red, iron red, molybdenum chrome red, ultramarine blue, chrome green, carbon black; organic pigments, such as Lisol Baohong BK, lake red C, blush, Jiaji R red, turnip red, permanent magenta HF3C, plastic red R and clomo red BR, permanent orange HL, fast yellow G, Ciba plastic yellow R, permanent yellow 3G, permanent yellow H ₂ G, indigo blue B, indigo green, plastic purple RL, aniline black; organic dyes, such as thioindigo, reduced yellow 4GF, Shilin blue RSN, salt-based rose essence, oil-soluble yellow, etc.; wherein the colorant is selected according to the color requirements of the sample, without special limitation . The amount of the coloring agent to be used is not particularly limited and is usually from 0.3 to 0.8% by weight.

The fluorescent whitening agent in the auxiliary agent can obtain the effect of the fluorite-like glittering of the dyed substance, including but not limited to any one or any of the following fluorescent whitening agents: stilbene type, a coumarin type, a pyrazoline type, a benzoxyl type, a phthalimide type, etc., wherein the fluorescent whitening agent is preferably sodium stilbene biphenyl disulfonate (fluorescent whitening agent CBS), 4 , 4-bis(5-methyl-2-benzoxazolyl)stilbene (fluorescent brightener KSN), 2,2-(4,4'-distyryl)bisbenzoxazole (fluorescence Brightener OB-1). The amount of the fluorescent whitening agent to be used is not particularly limited and is usually from 0.002 to 0.03 % by weight.

The matting agent in the auxiliary agent enables diffuse reflection when incident light reaches the surface of the polymer, resulting in a low-gloss matt and matte appearance, including but not limited to any one or any of the following matting agents: The precipitated barium sulfate, silica, hydrous gypsum powder, talc powder, titanium dioxide, polymethyl urea resin and the like; wherein the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited and is usually from 2 to 5% by weight.

The flame retardant in the auxiliary agent can increase the flame resistance of the material, including but not limited to any one or any of the following flame retardants: phosphorus, such as red phosphorus, tricresyl phosphate, triphenyl phosphate Ester, tricresyl phosphate, toluene diphenyl phosphate; halogen-containing phosphates such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl) phosphate; organic halide Such as high chlorine content chlorinated paraffin, 1,1,2,2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentanane; inorganic flame retardants, such as antimony trioxide, aluminum hydroxide , magnesium hydroxide, zinc borate; reactive flame retardants, such as chloro-bromic anhydride, bis(2,3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride Etc.; wherein the flame retardant is preferably decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate, antimony trioxide. The amount of the flame retardant to be used is not particularly limited and is usually from 1 to 20% by weight.

The nucleating agent in the auxiliary agent can shorten the crystallization rate, increase the crystal density and promote the grain size miniaturization by changing the crystallization behavior of the polymer, thereby shortening the material molding cycle, improving the transparency, surface gloss and resistance of the product. The purpose of physical and mechanical properties such as tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, etc., including but not limited to any one or any of the following nucleating agents: benzoic acid, adipic acid, sodium benzoate , talc, sodium p-phenolate, silica, dibenzylidene sorbitol and its derivatives, ethylene propylene rubber, ethylene propylene diene rubber, etc.; wherein, the nucleating agent is preferably silica, dibenzylidene pear Sugar alcohol (DBS), EPDM rubber. The amount of the nucleating agent to be used is not particularly limited and is usually from 0.1 to 1% by weight.

The rheological agent in the auxiliary agent can ensure good paintability and appropriate coating thickness of the polymer in the coating process, prevent sedimentation of solid particles during storage, and can improve redispersibility thereof, including However, it is not limited to any one or any of the following rheological agents: inorganic substances such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, fumed silica, water Glass, colloidal silica; organometallic compounds such as aluminum stearate, aluminum alkoxides, titanium chelate, aluminum chelate; organic, such as organic bentonite, hydrogenated castor oil / amide wax, isocyanate derivatives, An acrylic emulsion, an acrylic copolymer, a polyethylene wax, a cellulose ester or the like; wherein the rheological agent is preferably an organic bentonite, a polyethylene wax, a hydrophobically modified alkaline swellable emulsion (HASE), or an alkali swellable emulsion (ASE). The amount of the rheology agent to be used is not particularly limited and is usually from 0.1 to 1% by weight.

The thickener in the auxiliary agent can impart good thixotropy and proper consistency to the polymer mixture, thereby satisfying various requirements such as stability energy and application performance during production, storage and use. Including but not limited to any one or any of the following thickeners: low molecular substances such as fatty acid salts, alkyl dimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, dehydrated sorbus Alcohol tricarboxylate, glycerol trioleate, cocoamidopropyl betaine, titanate coupling agent; high molecular substances, such as bentonite, artificial hectorite, fine powder silica, colloidal aluminum, animal protein, Polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, crotonic acid copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, etc.; wherein the thickener is preferably hydroxy coconut oil diethanolamide, acrylic acid - A methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited and is usually from 0.1 to 1.5% by weight.

The leveling agent in the auxiliary agent can ensure the smoothness and uniformity of the polymer coating film, improve the surface quality of the coating film, and improve the decorative property, including but not limited to any one or any of the following leveling agents: Dimethylsiloxane, polymethylphenylsiloxane, polyacrylate, silicone resin, etc.; among them, the leveling agent is preferably polydimethylsiloxane or polyacrylate. The amount of the leveling agent to be used is not particularly limited and is usually from 0.5 to 1.5% by weight.

In the preparation of the dynamic covalent polymer, the auxiliary agent is preferably a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a chain extender, a toughener, a plasticizer, a foaming agent, Flame retardant, dynamic regulator.

The filler mainly plays the following roles in the dynamic covalent polymer: 1 reducing the shrinkage rate of the molded article, improving the dimensional stability, surface smoothness, smoothness, and flatness or mattness of the product; The viscosity of the polymer; 3 to meet different performance requirements, such as improving the impact strength and compressive strength of the polymer material, hardness, stiffness and modulus, improving wear resistance, increasing heat distortion temperature, improving conductivity and thermal conductivity; The coloring effect; 5 imparts light stability and chemical resistance; 6 plays a compatibilizing effect, which can reduce the cost and improve the competitiveness of the product in the market.

The filler is selected from any one or any of the following fillers: an inorganic non-metallic filler, a metal filler, and an organic filler.

The inorganic non-metallic filler includes, but is not limited to, any one or more of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon, quartz, mica powder, clay, Asbestos, asbestos fiber, feldspar, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotubes, molybdenum disulfide, slag, flue ash, wood flour and shell powder , diatomaceous earth, red mud, wollastonite, silicon aluminum black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, niobium Stone, iron mud, white mud, alkali mud, (hollow) glass beads, foamed microspheres, foamable particles, glass powder, cement, glass fiber, carbon fiber, quartz fiber, carbon fiber boron fiber, titanium diboride Fiber, calcium titanate fiber, silicon carbide fiber, ceramic fiber, whisker, and the like. In one embodiment of the present invention, an inorganic non-metallic filler having conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fiber, is preferably used to conveniently obtain a composite having electrical conductivity and/or electrothermal function. material. In another embodiment of the present invention, it is preferred to have a non-metallic filler having a heat generating function under the action of infrared and/or near-infrared light, including but not limited to graphene, graphene oxide, carbon nanotubes, and convenient use of infrared rays. Composite materials that are heated by and/or near-infrared light. Good heat generation performance, especially remote control heat generation, is beneficial to the polymer to obtain controllable shape memory, self-healing and other properties. In another embodiment of the present invention, an inorganic non-metallic filler having thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, and a composite for facilitating thermal conductivity is preferred. material.

The metal filler, including metal compounds, including but not limited to any one or any of the following: metal powder, fiber, including but not limited to powders, fibers of copper, silver, nickel, iron, gold, etc. and alloys thereof Nano metal particles, including but not limited to nano gold particles, nano silver particles, nano palladium particles, nano iron particles, nano cobalt particles, nano nickel particles, nano Fe ₃ O ₄ particles, nano γ-Fe ₂ O ₃ particles, Nano-MgFe ₂ O ₄ particles, nano-MnFe ₂ O ₄ particles, nano-CoFe ₂ O ₄ particles, nano-CoPt ₃ particles, nano-FePt particles, nano-FePd particles, nickel-iron bimetallic magnetic nanoparticles and others in infrared, near-infrared, ultraviolet At least one kind of nano metal particles that can generate heat under electromagnetic action; liquid metal, including but not limited to mercury, gallium, gallium indium liquid alloy, gallium indium tin liquid alloy, other gallium-based liquid metal alloy; metal organic compound molecule, Crystals and other substances that can generate heat under at least one of infrared, near-infrared, ultraviolet, and electromagnetic. In one embodiment of the present invention, can be preferably electromagnetic and / or near-infrared heating fillers, including but not limited to nano-gold, nano silver, nano Pd, nano Fe ₃ O _4, for sensing heat. In another embodiment of the present invention, a liquid metal filler is preferred to facilitate obtaining a composite material having good thermal conductivity, electrical conductivity, and ability to maintain flexibility and ductility of the substrate. In another embodiment of the present invention, the organometallic compound molecules and crystals which can generate heat under at least one of infrared, near-infrared, ultraviolet, and electromagnetic are preferable, and on the one hand, the composite is facilitated, and the other side is improved in the efficiency of inducing heat generation and heating. effect.

The organic filler includes, but is not limited to, any one or more of the following: fur, natural rubber, synthetic rubber, synthetic fiber, synthetic resin, cotton, cotton linters, hemp, jute, linen, asbestos, cellulose, acetic acid Cellulose, shellac, chitin, chitosan, lignin, starch, protein, enzyme, hormone, lacquer, wood flour, shell powder, glycogen, xylose, silk, rayon, vinylon, phenolic microbeads, Resin beads, etc.

Wherein, the type of the filler is not limited, and is mainly determined according to the required material properties, and preferably calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass microbeads, foamed microspheres, and glass fibers. The amount of the filler used for the carbon fiber, the metal powder, the natural rubber, the chitosan, the protein, and the resin microbead is not particularly limited and is usually from 1 to 30% by weight.

In the preparation of the dynamic covalent polymer, the dynamic covalent polymer can be prepared by mixing a certain ratio of the materials by any suitable material mixing method known in the art, which can be a batch, semi-continuous or continuous process. Formal mixing; likewise, dynamic covalent polymers can be formed in a batch, semi-continuous or continuous process. The mixing modes employed include, but are not limited to, solution agitation mixing, melt agitation mixing, kneading, kneading, opening, melt extrusion, ball milling, etc., wherein solution agitation mixing, melt agitation mixing, and melt extrusion are preferred. The form of energy supply during material mixing includes, but is not limited to, heating, illumination, radiation, microwave, ultrasound. The molding methods used include, but are not limited to, extrusion molding, injection molding, compression molding, tape casting, calender molding, and casting molding.

In the preparation of the dynamic covalent polymer, other polymers, auxiliaries, and fillers which may be added/used as described above may be added to form a dynamic covalent polymer composite system, but these additions/uses are not It is all necessary.

A specific method for preparing a dynamic covalent polymer by stirring and mixing the solution is usually carried out by stirring and dispersing the raw materials in a dissolved or dispersed form in a respective solvent or a common solvent in a reactor. Usually, the mixing reaction temperature is controlled at 0 to 200 ° C, preferably 25 to 120 ° C, more preferably 25 to 80 ° C, and the mixing and stirring time is controlled to be 0.5 to 12 h, preferably 1 to 4 h. The product obtained after the mixing and stirring may be poured into a suitable mold and placed at 0 to 150 ° C, preferably 25 to 80 ° C, for 0 to 48 hours to obtain a polymer sample. In this process, a solvent sample may be selected as a solution, an emulsion, a paste, a gel, or the like, or a solid solution in the form of a film, a block, a foam, or the like may be selected as a solvent. Polymer sample. When preparing a dynamic covalent polymer by this method, it is usually necessary to add an initiator in a solvent to initiate polymerization to obtain a dynamic covalent polymer by solution polymerization, or to add a dispersing agent and an oil-soluble initiator to prepare a suspension. The polymerization is initiated by suspension polymerization or slurry polymerization to obtain a dynamic covalent polymer, or an initiator and an emulsifier are added to prepare an emulsion to initiate polymerization by emulsion polymerization to obtain a dynamic covalent polymer. The methods of solution polymerization, suspension polymerization, slurry polymerization, and emulsion polymerization employed are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be further developed here.

The solvent used in the above preparation method should be selected according to the actual conditions such as the reactants, products and reaction processes, including but not limited to any one of the following solvents or a mixed solvent of any of 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, citrate buffer, acetic acid Buffer solution, phosphate buffer solution, boric acid buffer solution, etc.; preferably deionized water, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, dimethylformamide, phosphate buffer solution. In addition, the solvent may also be selected from the group consisting of an oligomer, a plasticizer, and an ionic liquid; the oligomer includes, but is not limited to, a polyethylene glycol oligomer, a polyvinyl acetate oligomer, and a polybutyl acrylate. a polymer, a liquid paraffin or the like; the plasticizer may be selected from the class of plasticizers in the additive which may be added, and is not described herein; the ionic liquid generally consists of an organic cation and an inorganic anion. The cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphonium ion, a 1,3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion, etc.; the anion is usually a halogen ion, a tetrafluoroborate ion, and a hexa Fluoride ions, also CF ₃ SO ₃ ^- , (CF3SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , C ₄ F ₉ SO ₃ ^- , CF ₃ COO ^- , (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , SbF ₆ ^- , AsF ₆ ^-, and the like. Wherein, using a deionized water to prepare a dynamic covalent polymer and selectively retaining it, a hydrogel can be obtained; when an organic solvent is used to prepare a dynamic covalent polymer and it is selected to be retained, an organogel can be obtained; When the oligomer is used to prepare a dynamic covalent polymer and is selected to retain it, an oligomer swollen gel can be obtained; when a dynamic covalent polymer is prepared by using a plasticizer and selected to be retained, a plasticizer can be obtained to swell. Gel; an ionic liquid swollen gel can be obtained by using an ionic liquid to prepare a dynamic covalent polymer and optionally retaining it.

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

A specific method for preparing a dynamic covalent polymer by melt-mixing, usually by directly stirring or mixing the raw materials in a reactor, and then stirring and mixing the mixture, generally in the form of a gas, a liquid or a solid having a lower melting point. Use in case. Usually, the mixing reaction temperature is controlled at 0 to 200 ° C, preferably 25 to 120 ° C, more preferably 25 to 80 ° C, and the mixing and stirring time is controlled to be 0.5 to 12 h, preferably 1 to 4 h. The product obtained after the mixing and stirring may be poured into a suitable mold and placed at 0 to 150 ° C, preferably 25 to 80 ° C, for 0 to 48 hours to obtain a polymer sample. When a dynamic covalent polymer is prepared by this method, it is usually necessary to add a small amount of an initiator to initiate polymerization to obtain a dynamic covalent polymer by melt polymerization or gas phase polymerization. The methods of melt polymerization and gas phase polymerization used are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be developed in detail here.

A specific method for preparing a dynamic covalent polymer by melt extrusion mixing is usually carried out by adding a raw material to an extruder for extrusion blending at an extrusion temperature of 0 to 280 ° C, preferably 50 to 150 ° C. The reaction product can be directly cast into a suitable size, or the obtained extruded sample can be crushed and then sampled by an injection molding machine or a molding machine. The injection temperature is 0-280 ° C, preferably 50-150 ° C, the injection pressure is preferably 60-150 MPa; the molding temperature is 0-280 ° C, preferably 25-150 ° C, more preferably 25-80 ° C, the molding time is 0.5-60 min, preferably The molding pressure is preferably 4-15 MPa at 1-10 min. The spline can be placed in a suitable mold and placed at 0-150 ° C, preferably 25-80 ° C, for 0-48 h to give the final polymer sample.

In the preparation of the dynamic covalent polymer, the molar equivalent ratio of the selected inorganic boron compound to the silicon-containing hydroxy group-containing siloxane compound should be in an appropriate range, and the molarity of other reactive groups for the polymerization/crosslinking reaction is carried out. The equivalent ratio is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, still more preferably in the range of 0.8 to 1.2. In the actual preparation process, those skilled in the art can adjust according to actual needs.

In the preparation of the dynamic covalent polymer, the amount of the raw materials of the components of the dynamic covalent polymer is not particularly limited, and those skilled in the art can adjust according to the actual preparation conditions and the properties of the target polymer.

The dynamic covalent polymer has a wide range of properties, and has broad application prospects in military aerospace equipment, functional coatings and coatings, biomedical materials, energy, construction, bionics, smart materials and the like.

By utilizing the dilatancy of dynamic covalent polymers, it can be applied to oil well production, fuel explosion protection, etc., and can also be used to prepare speed lockers for roads and bridges. When the polymer material is subjected to vibration, it can dissipate a large amount of energy to dampen the effect, thereby effectively mitigating the vibration of the vibrating body. It can be applied to the production of damping dampers for various motor vehicles, mechanical equipment, bridges, The vibration isolation of the building; as an energy absorbing cushioning material, it is applied to cushioning packaging materials, sports protective products, impact protection products, and military and police protective materials to reduce the shock and impact of objects or human body under external force. , including shock waves generated by explosions; as energy absorbing materials, it can also be used for sound insulation, noise reduction, etc.; it can also be used to make seismic shear plates or cyclic stress bearing tools, or for making stress monitoring sensors. The dynamic covalent bond, the strength and dynamic difference of the supramolecular hydrogen bond can also be used as a shape memory material; the stress can be prepared by the dynamic reversibility and stress rate dependence of the dynamic covalent polymer. A part of sensitive polymer materials can be used to make toys and fitness materials with magical effects of fluidity and elastic conversion. When the inorganic boronic acid silicate bond is used as a sacrificial bond, it can impart excellent toughness to the polymer material by absorbing a large amount of energy under an external force, thereby obtaining a polymer film, fiber or sheet having excellent toughness. Widely used in military, aerospace, sports, energy, construction and other fields.

Based on the dynamic reversibility of inorganic boronic acid silicate bond and suitable component selection and formulation design, it is also possible to design and prepare self-repairing preparations, coatings, films, sheets, profiles, plates and the like. For example, by making full use of the self-healing properties of dynamic covalent polymers, it is possible to prepare a self-repairing adhesive for use in the adhesion of various materials, as a bulletproof glass interlayer adhesive, or for preparation with Good plasticity and recovery of repaired polymer plugging adhesive; based on the dynamic reversibility of inorganic boronic acid silicate bond, it is possible to design a scratch-resistant coating with self-repairing function, thereby prolonging the service life of the coating and realizing the matrix Long-lasting corrosion protection of materials; through suitable component selection and formulation design, polymer gaskets or polymer sheets with self-healing properties can be prepared, which can mimic the principle of damage healing of organisms, enabling materials to be internal or external The damage is self-healing, eliminating hidden dangers, prolonging the service life of materials, and showing great application potential in the fields of military industry, aerospace, electronics, and bionics.

The dynamic covalent polymers of the present invention are further described below in connection with some specific embodiments. The specific embodiments are intended to describe the invention in further detail, without limiting the scope of the invention.

Example 1

Mixing oligomeric polymethylhydrogensiloxane (PHMS, molecular weight 500) with acryloyloxy-ceicosyltrimethoxysilane to control the active hydrogen atoms in the polymethylhydrogensiloxane in the reaction (directly connected to Si) The ratio of the number of moles of the hydrogen atom to the number of moles of the acryloyloxymethyltrimethoxysilane double bond is about 1:1, and the addition reaction is carried out using chloroplatinic acid as a catalyst to obtain a trimethoxysilane having a side group. Group of organopolysiloxanes.

The above organopolysiloxane, hydroxyl terminated polydimethylsiloxane (molecular weight 700) and trimethyl borate according to the molar ratio of Si-OCH ₃ group, Si-OH group and B-OR group 1 :1:2 mixing, heating to 80 ° C and mixing uniformly, adding 4 ml of deionized water to 100 g of the mixture, adding a small amount of acetic acid dropwise, and then adding 1.0 g of graphene, 0.5 g of organic bentonite, under stirring A polymerization reaction is carried out to prepare a dynamic polymer containing an inorganic boronic acid silicate bond.

The obtained polymer sample is rubbery, can be stretched in a wide range at a slow stretching rate, and creeps; it is slow or unrecoverable after being lightly pressed with a finger; but if it is rapidly stretched or struck, it shows Elastic characteristics. Because its conductivity can respond sensitively to pressure or tension, it is suitable as a force sensor.

Example 2

a methoxy-terminated polymethylvinylsiloxane (molecular weight of about 20,000) and 2-tert-butoxycarbonylaminoethanethiol, 3-mercaptopropyltrimethoxysilane according to a double bond and two fluorenyl compounds Mixing at a molar ratio of 3:2:1, adding 0.2% by weight of photoinitiator benzoin dimethyl ether (DMPA) relative to 2-tert-butoxycarbonylaminoethanethiol, stirring well, and placing ultraviolet radiation in an ultraviolet cross-linker 4h, an organopolysiloxane containing a side hydrogen bond group was prepared.

The above-mentioned organopolysiloxane containing a side hydrogen bond group, 1,7-dichlorooctamethyltetrasiloxane and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate according to Si -OCH ₃ group, Si-Cl group and B-OR group molar ratio 1:1:2 mixed, take 100g mixture, warm to 80 ° C and mix well, add 4.2g microsphere foaming agent, 2g poly Ammonium phosphate, 4ml of deionized water, mixed rapidly for 30s, and then stirred for 4h in a nitrogen atmosphere to prepare a soft foamed polysiloxane containing a side hydrogen bond group and a silicon borate bond. material.

The reaction product was poured into a suitable mold, placed in a vacuum oven at 60 ° C for 24 hours, then cooled to room temperature for 30 minutes, and foamed by a flat vulcanizing machine, wherein the molding temperature was 140-150 ° C, molding time It is 10-15min, the pressure is 10MPa, the sample can be extended within a certain range and has good self-repairing function. It can be used as self-healing glass interlayer adhesive and has durability.

Example 3

Bis(3-methoxydiethylsilylpropyl)(Z)-but-2-enedioate and ethoxyboric acid are mixed at a molar ratio of 1:1, 100 g of the mixture is taken, and the temperature is raised to 80 ° C. A dynamic polymer containing a silicon borate bond was prepared by adding 10 ml of deionized water and conducting polymerization under stirring.

The product exhibits good dilatancy, good energy absorption, and can be used as a toy with magical elasticity.

Example 4

Boric acid and propenyldimethylchlorosilane were mixed at a molar ratio of 1:3, and triethylamine was used as a catalyst to carry out a reaction at 80 ° C for 12 hours to prepare a silicon borate compound 4 having a double bond at the end.

Ethyl isocyanate and an equimolar equivalent of propylene glycol monoallyl ether were dissolved in dichloromethane to give (allyloxy)propylethylcarbamate under triethylamine catalysis.

In a three-necked flask, 20 g of polyether dithiol, 6.8 g of the above-mentioned siliconic acid borate compound 4 with a double bond, 3.2 g of the above (allyloxy)propyl ethyl carbamate, and then placed in the ultraviolet Ultraviolet radiation in the instrument for 8 h gave a dynamic polymer containing a side hydrogen bond group and a silicon borate bond.

The polymer product can be slowly extended under external tensile stress to obtain a super-stretching effect (breaking elongation of up to 3000%). In the present embodiment, the prepared polymer sample can be used as a sandwich adhesive for bulletproof glass, which has the effect of dissipating stress under the impact force.

Example 5

The terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of β-diimine zinc to obtain polycarbonate PLimC.

The above polycarbonate PLimC and γ-mercaptopropylmethyldimethoxysilane, N-[(2-mercaptoethyl)carbamoyl]propanamide are 10:5:5 in terms of a double bond group and a thiol group. Mixing, adding 0.3 wt% of AIBN, a polycarbonate having a pendant group containing a hydrogen bond group and a methoxysilane group was obtained by a click reaction.

Weigh 45 g of the above-mentioned pendant group containing a hydrogen bond group and a methoxysilane group and 10 g of tris(2-methoxyethyl) borate, stir well and mix well, and then heat up to 80 ° C, then add 10ml of deionized water, add a small amount of acetic acid, add 2.5g of polymer foamed microspheres, 0.2mg of BHT antioxidant, stir rapidly by professional equipment to produce bubbles, then quickly inject into the mold and solidify at room temperature After 30 min, and then cured at 80 ° C for 4 h, a foam containing a side hydrogen bond group and a silicon borate bond was obtained.

The foam has good chemical resistance, and the obtained polymer material can be used as a substitute for glass products, a rigid packaging box, a decorative board, has toughness and durability, and has good self-healing property. And biodegradability.

Example 6

Mixing dimethylallyl chlorosilane and 1,10-fluorene dithiol in a molar ratio of 2:1, using AIBN as an initiator and triethylamine as a catalyst, thiol-ene click reaction to obtain dimethylene A propylchlorosilane-terminated silicon-containing compound.

The silicon-containing compound and boric acid were mixed at a molar ratio of 1:2, stirred well and uniformly mixed, and 100 g of the mixture was taken. After heating to 80 ° C, 4 ml of deionized water was added, and polymerization was carried out for 8 hours under stirring to prepare a A dynamic polymer containing a boron oxyboron bond and a silicon borate bond.

The polymer product has good dilatancy and can be used as a material for speed lockers.

Example 7

(1) mixing oligomeric polyvinyl alcohol (PVA) (molecular weight of about 500) with a certain amount of 3-isocyanatepropyltrimethoxysilane, using triethylamine as a catalyst, reacting in dichloromethane, controlling The ratio of the number of moles of PVA hydroxyl groups to the number of moles of isocyanate in the reaction is about 1:1.2, and a polyol oligomer having a pendant group containing a urethane group and a trimethoxysilyl group is obtained.

The above-mentioned polyol oligomer containing a urethane group and a trimethoxysilyl group and boric acid are mixed at a molar ratio of Si-OCH ₃ group and B-OH group of 1:1, and the temperature is raised to 80 ° C. After mixing uniformly, a small amount of 20% acetic acid solution was added dropwise, and polymerization was carried out for 8 hours under stirring, then 80 wt% of epoxidized soybean oil and 3 wt% of carbon nanotubes were added, and the mixture was sufficiently swollen for 24 hours, and then a kind of preparation was obtained. A side-hydrogen bond group and a silicon silicate bond-bonded epoxidized soybean oil-swelling dynamic polymer organogel.

In the present embodiment, the polymer organogel not only exhibits good mechanical properties, but also has self-repairing, pH response and other functional characteristics. The obtained organogel has excellent toughness.

Example 8

20 g of four-arm PEG with a trimethoxysilyl group at the end (molecular weight of about 25,000) and 3.2 g of diphenylhydroborate were mixed, heated to 80 ° C and stirred well, and then 4 ml of deionized water was added. The polymerization was carried out under stirring to prepare a dynamic polymer containing a silicon borate bond.

The dynamic polymer hydrogel can be obtained by further swelling the above dynamic polymer with deionized water. The dynamic polymer hydrogel has excellent self-healing properties and can be used as an aqueous medical dressing.

Example 9

Using allyl alcohol as initiator and stannous octoate as catalyst, ring-opening polymerization of ε-caprolactone is carried out to obtain olefin monocapped polycaprolactone, which is then acrylated to obtain olefin double-capped polycaprolactone. Then, it was combined with γ-mercaptopropyltrimethoxysilane with AIBN as initiator and triethylamine as catalyst to obtain trimethoxysilane-capped polycaprolactone by thiol-ene click reaction.

The above silane trimethoxysilane-terminated polycaprolactone and trimethyl borate are mixed 1:1 according to the molar ratio of Si-OCH ₃ group and B-OR group, and 20 g of the blend is taken, and the mixture is heated to 80 ° C and uniformly mixed. Thereafter, 4 ml of deionized water was added, and 1 mL of triethylamine and 200 mg of 200-mesh nanoclay were added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a silicon borate bond.

The resulting polymer sample can be stretched within a certain range. In addition, after the surface of the sample was slightly scratched, after applying a certain pressure for 2 hours in a mold at 50 ° C, the scratch disappeared and the self-healing effect was good. This polymer product can be used as a scratch-resistant and degradable packaging material.

Example 10

Polyhydroxyethyl acrylate (molecular weight of about 800) was obtained by free radical polymerization using hydroxyethyl acrylate as a monomer.

Mixing the above oligomeric polyhydroxyethyl acrylate with 2-mercaptoisothiocyanate and 3-isocyanatepropyltrimethoxysilane (by a hydroxyl group and isocyanate molar ratio of 2:1.1:1.1) to triethyl The amine is reacted as a catalyst in dichloromethane to obtain a polyacrylate having a pendant thiocarbamate group and a trimethoxysilane group.

The polyacrylate having a thiocarbamate group and a trimethoxysilyl group and a boric acid in the above-mentioned side group are mixed at a molar ratio of Si-OCH ₃ group and B-OH group by 1:1, and the temperature is raised to 80 ° C. After mixing uniformly, 2 g of white carbon black, 3 g of titanium dioxide, 1.5 g of cellulose crystallites, 2.2 g of ferric oxide were added, and polymerization was carried out for 8 hours under stirring to obtain a side-containing hydrogen bond group and a silicon borate. The dynamic polymer of the bond.

The polymer product can be used to prepare a polymer gasket or polymer sheet having a self-healing function.

Example 11

Styrene and styrene ethyltrimethoxysilane were mixed at a molar ratio of 2:1, and AIBN was used as an initiator to obtain a terminal siloxane-modified polystyrene by radical copolymerization. Weigh 15 g of the above terminal siloxane-modified polystyrene and 3.2 g of trimethyl borate in a dry clean beaker, pour 120 ml of toluene solvent into it, heat to 60 ° C, dissolve by stirring, and then The mixture was placed in a suitable mold and dried in a 60 ° C vacuum oven for 24 h to finally obtain a hard block polymer solid.

The product has high surface hardness and good mechanical strength, is heated in the mold to 180 ° C, molded under pressure of 5 MPa for 5 min, and made into a dumbbell shaped spline of 80.0 × 10.0 × 4.0 mm. Tensile test machine was used for tensile test. The tensile rate was 10mm/min. The tensile strength of the sample was 8.34±2.18MPa, and the tensile modulus was 19.45±2.57MPa. It has good chemical resistance and can be used. The obtained polymer material is used as a substitute for glass products and a rigid package.

Example 12

(1) 3-Aminopropylmethyldimethoxysilane and adipyl chloride are mixed at a molar ratio of 2:1, and triethylamine is used as a catalyst, and reacted in anhydrous dichloromethane to prepare a disiloxane seal. Terminal compound.

Weigh 8.0 g of the above disiloxane capping compound and 2.5 g of boric acid, and heat to 60 ° C for 8 h by stirring to obtain a dynamic polymer containing a silicon borate bond and a boron boron bond as the first network polymerization. Things.

(2) Allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidinone are dissolved in toluene by molar ratio 1:1, potassium carbonate is used as a catalyst, and tetrabutylammonium bromide is used as a phase transfer agent. An olefin monomer 12a containing an oxazolidinone group is obtained.

Under anhydrous and anaerobic conditions, the allyl mercaptan and 2-thiophene isocyanate are dissolved in methylene chloride at a molar ratio of 1:1, and catalyzed by triethylamine to obtain an olefin monomer 12b containing a thiourethane group.

The olefin monomer 12a olefin monomer 12b is thoroughly mixed at a molar ratio of 50:50, 80 parts of epoxy soybean oil is added, stirred well, and then swollen in the first network polymer, and then 5 mol% of AIBN is added, and the radical polymerization is carried out. An epoxidized soybean oil-swelling dynamic polymer organogel containing a side hydrogen bond group and a boronic acid borate bond and a boron boron bond is prepared.

This epoxidized soybean oil-swellable dynamic polymer organogel has soft elasticity and can be used to make an energy absorbing material.

Example 13

25 g of polyethylene glycol terminated at one end (molecular weight about 5000), 2 g of polyethylene glycol terminated at both ends (molecular weight about 2000) and 2.2 g of trimethyl borate were mixed, and the temperature was raised to 80 ° C to mix evenly. Then, 10 mL of deionized water and 100 mg of nano-silica having a particle size of 25 nm were added, ultrasonically dispersed for 1 h, and polymerization was carried out for 8 h under stirring to obtain a non-crosslinked dynamic polymerization containing a boronic borate bond and a boron boron bond. Things.

The polymer product can be used as an additive to lubricating oils to increase the service life of lubricating oils.

Example 14

The polybutadiene and fluorenylmethylmethyldiethoxysilane are mixed to maintain a molar ratio of alkenyl to fluorenyl group of 5:1, DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and side groups are obtained by click reaction. Silicone group-containing polybutadiene. Weigh 18 g of the above-mentioned pendant group siloxane group-containing polybutadiene and 4.7 g of tris(4-chlorophenyl)borate, and after heating to 60 ° C to dissolve by stirring, a small amount of 20% aqueous acetic acid solution was added to continue the reaction. At 4h, a dynamic polymer containing a silicon borate bond was obtained.

The polymer product can be used to prepare polymeric sealants that have good plasticity and can be recycled for repair.

Example 15

3-Chloropropyldimethylmethoxysilane and boric acid were mixed in an equimolar ratio, and after heating to 60 ° C to dissolve by stirring, a small amount of water was added for 3 hours to obtain a boric acid compound containing a boronic borate bond.

4,4'-bi-silyl phenyl alcohol and the above-mentioned boric acid compound containing a boronic acid borate bond are mixed in an equimolar ratio, 30 g of the mixture is taken, heated to 80 ° C, and then 10 mL of deionized water and 1.5 g of graphene oxide are added to continue the reaction. At 8 h, a non-crosslinked dynamic polymer containing a silicon borate bond was obtained.

The polymer product can be used to prepare a binder having a self-healing function.

Example 16

Trimethyl borate and dimethylmethoxy-3-butene silane were mixed at a molar ratio of 1:3, heated to 60 ° C and dissolved by stirring, and then a small amount of water was added to continue the reaction for 4 h to obtain a silyl borate. A trivinyl compound of the bond.

The above-mentioned trivinyl compound containing a boronic acid borate bond and trimethylolpropane tris(2-mercaptoacetate) are mixed at a molar ratio of 1:1, and placed in an ultraviolet cross-linker for ultraviolet light for 8 hours to obtain a kind. A dynamic polymer containing a silicon borate bond.

The polymer product can be used as a sheet or coating with self-healing and recyclability.

Example 17

A silane-grafted polyethylene is obtained by grafting methylvinyldiethoxysilane with low-density polyethylene using BPO as an initiator.

Weigh 5g of trimethyl borate, 65g of silane-grafted polyethylene (molecular weight of about 6000), 35g of low-density polyethylene, 8g of decabromodiphenylethane, 2g of antimony trioxide, 1g of anti-drip agent of polytetrafluoroethylene 1.0 g of dicumyl peroxide, 1 g of stearic acid, 0.2 g of antioxidant 1010, 0.2 g of di-n-butyltin dilaurate, and 0.5 g of dimethyl silicone oil were uniformly mixed, and the temperature was raised to 150 ° C, and the pressure was 15 MPa. After molding for 15 min, the prepared sample was placed in water at 90 ° C for 2 h, then taken out, placed in a mold, and left to stand under nitrogen protection at 120 ° C for 4 h to obtain a polyvinyl material containing a silicon borate bond. .

The polymer product can be reshaped to reflect recyclability. And it has excellent comprehensive performance, showing good mechanical strength and impact resistance, and can be used as an impact resistant material.

The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, The same is included in the scope of patent protection of the present invention.

Claims

a dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is linked to three -O-, and wherein it is dynamically covalently covalent with at least two BO-Si based on different B atoms The linker to which the different Si atoms in the bond are bonded contains a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.
a dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is linked to three -O-, and wherein it is dynamically covalently covalent with at least two BO-Si based on different B atoms The linker to which the different Si atoms in the bond are bonded is a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.
a dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is bonded to three -O-, and wherein at least two different BO-Si dynamic covalent bonds are present The linker to which any of the different Si atoms are attached is a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.
a dynamic covalent polymer characterized by comprising a BO-Si dynamic covalent bond, wherein any one B atom is bonded to three -O-, and wherein the Si atom phase in any different BO-Si dynamic covalent bond Any divalent linkage and its divalent or higher linkage are a linker L containing a carbon atom on the backbone of the dynamic covalent polymer backbone.
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the linking group L is selected from the group consisting of a hydrocarbon group, a polyolefin group, a polyether group, a polyester group, a polyurethane group, and a polyurea group. , polythiourethane group, polyacrylate group, polyacrylamide group, polycarbonate group, polyethersulfone group, polyarylsulfone group, polyetheretherketone group, polyimide group, polyamide group, poly Amine group, polyphenylene ether group, polyphenylene sulfide group, polyphenylsulfone group.
The dynamic covalent polymer according to any one of claims 1 to 4, which further contains a B-O-B bond.
The dynamic covalent polymer according to any one of claims 1 to 4, characterized in that it or a composition containing the same also contains hydrogen bonding; said hydrogen bonding, which is involved by a hydrogen bonding group form.
The dynamic covalent polymer according to claim 7, wherein said hydrogen bonding group contains both a hydrogen bond acceptor and a hydrogen bond donor.
The dynamic covalent polymer according to claim 8, wherein said hydrogen bond acceptor comprises at least one of the structures represented by the following formula:

Wherein A is selected from the group consisting of an oxygen atom and a sulfur atom; D is selected from a nitrogen atom and a C-R group; X is a halogen atom; and R is selected from a hydrogen atom, a substituted atom, and a substituent.
The dynamic covalent polymer according to claim 8, wherein said hydrogen bond donor contains at least one of the structures represented by the following formula:
The dynamic covalent polymer according to claim 7, wherein said hydrogen bonding group contains at least one of the following structural components:
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the composition or the composition thereof has any of the following properties: solution, emulsion, paste, gel, ordinary solid, elastomer ,foam.
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the B-O-Si dynamic covalent bond is formed by reacting an inorganic boron compound with a silicon-containing compound.
The dynamic covalent polymer according to claim 13, wherein the inorganic boron compound is selected from the group consisting of boric acid, boric acid esters, boric acid salts, boric anhydrides, and boron halides.
The dynamic covalent polymer according to claim 13, wherein the silicon-containing compound means that at least one of the terminal group and the side group of the compound contains a silanol group or a silanol precursor group. At least one; wherein the silanol group refers to a structural unit composed of a silicon atom and a hydroxyl group connected to the silicon atom; wherein the silanol precursor is referred to as a structural unit composed of a silicon atom and a group capable of hydrolyzing a hydroxyl group attached to the silicon atom, wherein a group capable of hydrolyzing to obtain a hydroxyl group selected from the group consisting of halogen, cyano, oxycyano, thiocyano, Alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoximino, alkoxide groups.
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the dynamic covalent polymer and its raw material component have one or more glass transition temperatures, or no glass transition a temperature; wherein the dynamic polymer and its raw material component have a glass transition temperature of at least one below 0 ° C, or between 0-25 ° C, or between 25-100 ° C, or above 100 °C.
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the polymer chain topology in the dynamic covalent polymer molecule or its raw material component is selected from the group consisting of a linear type, a ring, and a branch. , clusters, infinite network cross-linking structures, and combinations of the above.
The dynamic covalent polymer according to any one of claims 1 to 4, wherein the constituent component of the composition further comprises any one or any of the following additives: other polymers, auxiliaries, filler;

Wherein, the other polymer is selected from any one or more of the following: a natural polymer compound, a synthetic resin, a synthetic rubber, a synthetic fiber;

Wherein, the auxiliary agent is selected from any one or more of the following: a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a chain extender, a toughening agent, a coupling agent, a lubricant, Release agent, plasticizer, foaming agent, dynamic regulator, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, nucleating agent, rheological agent, increase Thickener, leveling agent;

Wherein, the filler is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
The dynamic covalent polymer according to any one of claims 1 to 4, which is applied to the following products: shock absorber, cushioning material, sound insulating material, sound absorbing material, impact resistant protective material, sports protection Products, military and police protective products, self-healing coatings, self-healing sheets, self-healing adhesives, bulletproof glass interlayer adhesives, energy storage device materials, ductile materials, shape memory materials, seals, toys, force sensors.
A method of absorbing energy, characterized in that a dynamic covalent polymer is provided and energy is absorbed as an energy absorbing material, wherein the dynamic covalent polymer contains a BO-Si dynamic covalent bond, wherein any a B atom is bonded to three -O-, and wherein a linking group which is bonded to at least two different Si atoms in a BO-Si dynamic covalent bond based on a different B atom contains a linking group L, said linking group L contains a carbon atom on the backbone of the dynamic covalent polymer backbone.