WO2018028365A1

WO2018028365A1 - Dynamic polymer with hybrid cross-linked network and application thereof

Info

Publication number: WO2018028365A1
Application number: PCT/CN2017/092131
Authority: WO
Inventors: 张欢; 李政; 徐晖; 梁愫; 翁文桂
Original assignee: 翁秋梅
Priority date: 2016-08-09
Filing date: 2017-07-07
Publication date: 2018-02-15
Also published as: CN107698748B; CN107698748A

Abstract

A dynamic polymer having a hybrid cross-linked network structure, which comprises covalent cross-linking and supramolecular hydrogen bond cross-linking; the covalent cross-linking is achieved by bonding exchangeable covalent bonds, and the supramolecular hydrogen bond cross-linking is achieved by a side group of a polymer chain backbone and/or hydrogen-bond groups on a side chain and optionally hydrogen-bond groups on a chain backbone. The polymer combines supramolecular dynamic features and vitrimer dynamic covalent features. The supramolecular hydrogen bond affords the material stimulus responsiveness, energy dissipation and self-healing properties. The bonding exchangeable covalent bond provides the structural stability and mechanical strength of cross-linked polymer, and at the same time enables the polymer to have features such as self-healing, recyclability, reproducibility due to the dynamic reversibility thereof. The dynamic polymer having a hybrid cross-linked network structure can be widely applied in shock absorbing materials, impact protection materials, self-healing materials, ductile materials, sealing parts, and so on.

Description

[Name of invention established by ISA in accordance with Rule 37.2] Dynamic polymers with hybrid crosslinked networks and their applications

Technical field

The present invention relates to a dynamic polymer of a hybrid crosslinked network, and more particularly to a dynamic polymer containing covalent cross-linking and supramolecular hydrogen bonding cross-linking of a bondable exchangeable covalent bond and its use.

Background technique

Conventional thermoplastic polymer materials are non-crosslinked polymers that undergo flow deformation when heated and retain a certain shape after cooling. Most thermoplastic polymer materials have the ability to be repeatedly heated and softened and cooled and hardened over a range of temperatures, making extrusion, injection, blow molding and welding easy. Therefore, thermoplastic materials can be reprocessed and recycled. On the other hand, a large number of thermoplastic polymer materials are also susceptible to creep due to non-crosslinked structures, resulting in poor structural stability and very limited mechanical properties. By introducing supramolecular hydrogen bonding in a thermoplastic polymer, the mechanical properties of the material, such as thermoplastic nylon and polyurethane materials, can be improved. However, in addition to improving mechanical properties to some extent, hydrogen bonding usually plays a very limited role.

A thermosetting polymer material can be obtained by forming a three-dimensional infinite network structure by forming intermolecular covalent bond crosslinks between polymer chains. Thermoset polymer materials have excellent mechanical properties, thermal stability and chemical resistance. However, since the thermosetting material is crosslinked by covalent bonding, as long as the polymerization reaction is completed, the breaking of the bond becomes very difficult, and the properties of the material are also immobilized. Therefore, traditional thermosetting materials cannot be recycled and recycled.

How to obtain excellent mechanical properties and structural stability, while being self-healing, recyclable and recyclable, and having polymer materials that stimulate responsiveness, especially stress and strain response, is currently a major challenge.

Summary of the invention

In view of the above background, the present invention provides a dynamic polymer having a hybrid crosslinked network structure. Wherein, covalent bond cross-linking and supramolecular hydrogen bond cross-linking are included; wherein the covalent bond cross-linking is achieved by a binding exchangeable covalent bond.

The dynamic polymer structure based on the covalent bond and the supramolecular hydrogen bond hybrid crosslinked network structure of the invention has good structural stability, good response to stress/strain, and biomimetic mechanical properties; Under the conditions of the glass-like dynamic reversibility, with processability and recyclability.

The invention is implemented by the following technical solutions:

The invention relates to a dynamic polymer having a hybrid crosslinked network, characterized in that it comprises covalent cross-linking and supramolecular hydrogen bonding cross-linking, and covalent cross-linking reaches covalent cross-linking in at least one network structure Above the gel point; the covalently crosslinked network backbone chain comprises at least one bound exchangeable covalent bond, which is necessary to form/maintain a covalent crosslinked structure of the dynamic polymer a condition; comprising a nucleophilic group for performing a binding exchangeable covalent bond exchange reaction; said hydrogen bonding cross-linking through a side hydrogen bond present on a side chain, a side chain or a side group and a side chain of the polymer chain The group and optionally the backbone hydrogen bonding group present on the polymer chain backbone are formed; the composition of which contains the catalyst required for the binding exchangeable covalent exchange reaction.

In an embodiment of the invention, the binding exchangeable covalent bond is selected from the group consisting of an exchangeable ester bond, a thioester bond, a dithioester bond, a carbonate bond, an amide bond, a urethane bond, sulfur A urethane bond, a vinyl amide bond, a vinyl urethane bond, an ethylene thiocarbamate bond, or the like. It is characterized in that it contains at least one of the structures represented by the following general formulae (1) and (2):

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R ₁ and R ₂ are absent;

When X is N, R _{1 is} present, R ₂ is absent; and R _{1 is} selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C or Si, R ₁ and R ₂ are present, and R ₁ and R ₂ are each independently selected from a hydrogen atom, a substituted atom, and a substituent; wherein R ₁ and R ₂ may be the same or different.

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the acceptor of the hydrogen bond group preferably contains at least one of the structures represented by the following formula (3):

Wherein A is selected from the group consisting of an oxygen atom and a sulfur atom; and D is selected from the group consisting of a nitrogen atom and a CR group. Wherein R is selected from a hydrogen atom, a substituted atom, and a substituent. In the present invention, A is preferably an oxygen atom, and D is preferably a CR group;

Wherein the donor of the hydrogen bond group contains a structure represented by the following formula (4):

In one embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network has only one network (the first network structure), characterized in that the covalent cross-linking in the network reaches above the covalent gel point; Wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming/maintaining a covalent crosslinked structure of the dynamic polymer; a pendant group of the polymer chain backbone and/or The side hydrogen bond group is present on the side chain. The polymer maintains an equilibrium structure by covalent crosslinking reaching above the gel point, providing supramolecular hydrogen bonding crosslinks by hydrogen bonding between the side hydrogen bonding groups. In this embodiment, covalent cross-linking containing a bound exchangeable covalent bond is used to provide a balanced structure in which exchangeable covalent bonds provide covalent dynamics; hydrogen bonding by the formation of pendant hydrogen bonding groups provides additional Supramolecular crosslinks and supramolecular dynamics.

In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks (second network structure), characterized in that covalent cross-linking in the first network reaches covalent Above the crosslinked gel point, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming/maintaining a dynamic polymer covalent crosslinked structure; The side and side chains do not contain the side hydrogen bond group; the second network does not contain covalent crosslinks, but there are side hydrogen bond groups on the side groups and/or side chains of the polymer chain; In this case, the equilibrium structure and covalent dynamics are maintained by covalent cross-linking in the first network, and supramolecular dynamics are provided by side hydrogen bonding in the second network.

In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks (a third network structure), characterized in that covalent cross-linking in the first network reaches a covalent price. Above the crosslinked gel point, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming/maintaining a dynamic polymer covalent crosslinked structure; The side and side chains do not contain the side hydrogen bonding group; the second network is the first network. In the network structure, the covalent crosslinks are maintained by the covalent crosslinks in the first network and the second network, and the bond exchangeable covalent bonds therein provide covalent dynamics; the cross hydrogen bond crosslinks in the second network are provided Supramolecular dynamics.

In another embodiment of the present invention, the dynamic polymer of the hybrid cross-linking network is composed of two networks (fourth network structure), characterized in that the first network is the first network structure; The second network does not contain covalent cross-linking, but there are side hydrogen bonding groups on the side groups and/or side chains of the polymer chain; the side hydrogen bond groups between the first network and the second network can be mutually The phase forms a hydrogen bond. In the network structure, the covalent crosslinks are maintained by the covalent cross-linking in the first network, and the covalent bonds exchanged therein provide covalent dynamics; the cross-linking through the first and second networks provides super Molecular dynamics.

In another embodiment of the present invention, the dynamic polymer of the hybrid cross-linking network is composed of two networks (fifth network structure), characterized in that both the first network and the second network are the first type The structure described by the network, but the first and second networks described above are different. Such a difference may be, for example, a difference in the main structure of the polymer chain, a different crosslink density of the covalently crosslinked, a different exchangeable covalent bond, a different composition of the side chain of the polymer chain and/or a side chain, and polymerization. The hydrogen bond groups on the side chain and/or side chain of the chain are different. In this embodiment, by adjusting the structure of the first network and/or the second network, the purpose of accurately controlling the dynamic polymer performance can be achieved.

In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of three networks (sixth network structure), characterized in that covalent cross-linking in the first network reaches covalent Above the crosslinked gel point, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond crosslink, which is a necessary condition for forming/maintaining a dynamic polymer covalent crosslinked structure; But it does not contain a hydrogen bond group; the second network does not contain covalent crosslinks, but there are side hydrogen bond groups on the side groups and/or side chains of the polymer chain; the third network is the first type Network structure. In the network structure, the equilibrium structure is maintained by covalent cross-linking in the first network and the third network, and the bond exchangeable covalent bond therein provides covalent dynamics through side hydrogen bonds in the second and third networks. Crosslinking provides supramolecular dynamics.

In addition to the above embodiments of the six hybrid network structures, the present invention may have other various hybrid network structure implementations, and one embodiment may include three or more networks of the same or different, the same Different covalent crosslinks and/or different hydrogen bond crosslinks may be included in the network, including hydrogen bond crosslinks in which an optional backbone hydrogen bond group is involved. In special cases, the side hydrogen bonding groups in the covalently crosslinked network cannot form hydrogen bonds with each other, and it is necessary to form hydrogen bonds with other components added. Binding exchangeable covalent bonds are used to provide covalent dynamic properties including, but not limited to, glass-like plasticity and self-healing; hydrogen bonding of pendant hydrogen bonding groups and optional backbone hydrogen bonding groups serves as Reversible physical cross-linking provides additional strength to the polymer, while leveraging its good dynamic properties, imparting stress/strain responsiveness, super toughness, self-healing, shape memory and more. Those skilled in the art can implement the logic and the context of the present invention reasonably and effectively.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network, characterized in that the binding exchangeable covalent bond group is selected from the group consisting of an ester group, a thioester group, a carbonate group, and an amide group. A base, a carbamate group, a thiourethane group, a urea group, a vinyl amide group, a vinyl carbamate group, and a derivative thereof.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network, characterized in that the side group or the side chain or the side group and the side chain of the hybrid crosslinked network further comprise at least one of the following A nucleophilic group that undergoes a binding exchangeable covalent bond exchange reaction: a hydroxyl group, a thiol group, an amino group.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network, characterized in that, when a side hydrogen bonding group is present in a covalently crosslinked network, each of said two covalent crosses is averaged The segment between the joints contains not less than 0.1 of the side hydrogen bond groups.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network is characterized in that there are also carboxyl groups, fluorine groups, hydroxyl groups, amino groups, fluorenyl side groups for forming hydrogen bonds.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network, characterized in that the catalyst for transesterification is selected from the group consisting of acids and acid salts thereof, alkali metal of Group IA and compounds thereof , Group IIA alkali metal and its compound, aluminum metal and its compound, tin compound, group IVB element compound, anionic layer column compound, supported solid catalyst, organozinc compound, organic compound;

The catalyst for the amine exchange reaction is selected from the group consisting of aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzyl Hydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N,N'-diphenyl thiourea, bismuth trifluoromethanesulfonate, montmorillonite, ruthenium tetrachloride, Glutamine transaminase, divalent copper compound, trivalent iron compound.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network, characterized in that the state of the dynamic polymer is selected from the group consisting of solid polymers, ionic liquid gels, oligomer swollen gels, plasticizing Swelling gel, organogel, hydrogel, foam.

In an embodiment of the present invention, a dynamic polymer having a hybrid crosslinked network, characterized in that the raw material component constituting the dynamic polymer further comprises any one or any of the following additives: an auxiliary agent, Additives, fillers;

Wherein, the auxiliary agent and the additive which may be added are selected from any one or more of the following: a solvent, a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a toughening agent, a coupling agent, a lubricant, Release agent, plasticizer, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, bactericidal fungicide, dehydrating agent, nucleating agent, rheological agent, increase Thickener, thixotropic agent, leveling agent, chain extender, foam stabilizer, foaming agent;

Wherein, the filler that can be added is selected from any one or any of the following fillers: an inorganic non-metallic filler, a metal filler, and an organic filler.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network is applied to the following articles: shock absorbers, cushioning materials, impact resistant protective materials, sports protective articles, military and police protective articles, self-healing Coatings, self-healing sheets, self-healing adhesives, self-healing sealing materials, interlayer adhesives, ductile materials, self-adhesive toys, shape memory materials.

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

(1) A dynamic polymer having a hybrid crosslinked network of the present invention contains two kinds of dynamic elements: a bond exchangeable covalent bond and a supramolecular side hydrogen bond. The binding exchangeable covalent bond can be used on the one hand to provide a covalent cross-linking equilibrium structure of the material, ie dimensional stability and creep resistance; on the other hand, under certain conditions, a bond exchange reaction can occur, and a bond break occurs. And re-generation, but the cross-linking density of the covalent cross-linking network is basically unchanged, and the cross-linked polymer is thus converted from thermosetting to thermoplastic, and exhibits glass-like properties, and its viscosity change behavior is similar to that of molten glass during heating and shaping. It conforms to Arrhenius's law and gives the material excellent self-healing, plasticity and recyclability, especially by simply heating it to be arbitrarily complex and can be welded at will. In addition, a side hydrogen bond group containing both a hydrogen bond acceptor and an amino hydrogen bond donor can generate hydrogen bonds more efficiently than a simple hydroxyl group or an amino group or a sulfhydryl group, and the environmental responsiveness of hydrogen bonding is also more abundant; The supramolecular hydrogen bonding cross-linking is used on the one hand to crosslink the covalent crosslinks, and on the other hand to provide specific energy based on the properties and dynamics of its supramolecular weak bonds, which can give the material excellent energy dissipation. Performance, damping performance, self-healing and shape memory. This is not achievable in existing polymer systems.

(2) A dynamic polymer having a hybrid crosslinked network of the present invention has good controllability. By controlling the molecular structure, molecular weight and other parameters of the raw materials, dynamic polymers with different apparent characteristics, adjustable properties and wide applications can be prepared. Dynamic polymers with different dynamic reversibility can be prepared by controlling the type and number of binding exchangeable covalent bonds and side chain groups and/or side hydrogen bonding groups on the covalently crosslinked backbone chain. . By controlling the ratio of the combination of the exchangeable covalent bond and the supramolecular hydrogen bond cross-linking, a dynamic polymer with various mechanical strength, self-repairability, energy absorption and the like can be prepared. By adjusting the number of hydrogen bond donors and donors in the hydrogen bond group, the number and strength of the hydrogen bonds formed can be adjusted; the hydrogen bond of no more than four teeth has good dynamics, showing excellent stress/strain responsiveness. The higher the hydrogen bonding strength of the four teeth or more, the better the additional crosslinking strength can be provided, and the better the can be used as a sacrificial bond to better dissipate energy and provide toughness. The glass transition temperature and hydrogen bond dynamics of the polymer can be adjusted by adjusting the linking structure and length between the side hydrogen bond group and the backbone chain. This is difficult to achieve in traditional covalent cross-linking and supramolecular cross-linking systems.

These and other features and advantages of the present invention will become apparent from the description and appended claims appended claims.

Detailed ways

Hereinafter, the present invention will be described in detail.

The invention relates to a dynamic polymer having a hybrid crosslinked network, characterized in that it comprises covalent cross-linking and supramolecular hydrogen bonding cross-linking, and covalent cross-linking reaches covalent cross-linking in at least one network structure Above the gel point; covalent cross-linking network The backbone chain comprises at least one binding exchangeable covalent bond, the binding being exchangeable covalent bond as an aggregated or crosslinked linking point of the dynamic polymer or as both an aggregated linking point and a crosslinked linking point Exist, is a necessary condition for forming/maintaining a covalent cross-linking structure of a dynamic polymer; the hydrogen bond cross-links through a hydrogen bond group present on a side chain and/or a side chain of the polymer chain (hereinafter referred to as "side hydrogen bond" The "group" and optionally a hydrogen bond group (hereinafter referred to as "backbone hydrogen bond" group) present on the polymer chain backbone are formed.

The "polymerization" described in the present invention is a growth process/action of a chain, that is, a polymer which forms a linear, branched, cyclic, two-dimensional/three-dimensional cluster, three-dimensional infinite network structure by an intermolecular reaction. It should be noted that in the process of forming a ring, a two-dimensional/three-dimensional cluster, or a three-dimensional infinite network structure polymer, an intramolecular reaction may also be employed.

The term "crosslinking" as used in the present invention refers specifically to the process/action of forming a three-dimensional cluster and/or a three-dimensional network of infinite network structures, which can be understood as a special case of the above polymerization. In general, during the cross-linking process, the polymer chains grow in two-dimensional/three-dimensional directions, gradually forming clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite networks. In the cross-linking process, the reaction point that first reaches a three-dimensional infinite network is called the gel point (diafiltration threshold). In the present invention, "covalent cross-linking" means covalent cross-linking to reach a gel point or more unless otherwise specified; "hydrogen bond cross-linking" may be above or below the gel point of hydrogen bond cross-linking.

According to an embodiment of the present invention, the cross-linking action employs both a covalent form (structure) and a supramolecular form (structure). Wherein the covalently crosslinked network chain backbone comprises at least one bound exchangeable covalent bond; wherein the supramolecular crosslinked form is hydrogen bond crosslinking. Thus, the polymer network is referred to as a "hybrid crosslinked network." The "network" in the present invention means a "crosslinked network" unless otherwise specified.

In the embodiment of the present invention, the covalent cross-linking in the same system may have one or more, that is, any suitable covalent cross-linking topology, chemical structure, reaction mode, combination thereof, etc. may be employed, but The valence crosslink network backbone chain contains at least one bound exchangeable covalent bond and is a necessary condition for forming/maintaining a dynamic polymer covalent crosslinked structure. In the embodiment of the present invention, at least one cross-linking network in a system may be a single network, or may have multiple networks that are mutually blended, or may have multiple networks interpenetrating, or simultaneously There are blending and interpenetrating, and so on. Wherein, two or more networks may be the same or different; it may be that the partial network only contains a combination of covalent cross-linking and partial network only contains hydrogen bond cross-linking, or the part only contains covalent cross-linking and partial simultaneous inclusion. a combination of covalent cross-linking and hydrogen-bond cross-linking, or a combination comprising only a hydrogen bond cross-linking and a partial covalent cross-linking and hydrogen-bond cross-linking, or a covalent cross-linking in each network Crosslinking with hydrogen bonds, but the invention is not limited thereto; and in embodiments of the invention, the covalent cross-linking must reach above the gel point of covalent crosslinking in at least one network. Thus, for the polymer of the present invention, it is ensured that the polymer can maintain a balanced structure even in the case of only one network, that is, in a normal state, it can be (at least partially) insoluble in the unmelted solid. When there are multiple networks, different networks may have interactions, that is, supramolecular interactions, which may be independent of each other; and in addition to at least one network, the covalent cross-linking must reach above the gel point of covalent cross-linking, Crosslinking of other networks (including the sum of covalent and supramolecular hydrogen bond crosslinks) may be above the gel point or below the gel point, preferably above the gel point.

In embodiments of the invention, conventional covalent bonds are present in addition to the presence of at least one bound exchangeable covalent bond. The "conventional covalent bond" refers to a chemical bond that is unlikely to be broken at a normal temperature (generally not higher than 100 ° C) and within a usual time (generally less than 1 day), including but not limited to a carbon-carbon single bond, Ether bond, carbon nitrogen bond, and the like. The "binding exchangeable covalent bond" means that a characteristic chemical bond can be activated under certain conditions, and a bond exchange reaction occurs (eg, transesterification reaction, amide exchange reaction, carbamate exchange reaction, vinyl insertion). An amine exchange reaction of an amide or a vinyl carbamate, etc.). Wherein, the "binding bond exchange reaction" means that a new covalent bond is generated elsewhere and dissociated with the old covalent bond, thereby causing chain exchange and polymer topology change. For the purposes of the present invention, the crosslink density of the polymer network is substantially unchanged during this exchange process due to the specificity of the combined exchange reaction. Here, the "certain conditions" mean, in the presence of a suitable catalyst, heating conditions, pressurization conditions, and the like. Wherein, the "nucleophilic group" refers to a reactive group such as a hydroxyl group, a mercapto group and an amino group which are present in the polymer system for exchange reaction; if a transesterification reaction occurs, a carbamate exchange reaction requires a hydroxyl group to be reserved; Thioester exchange reaction, thiocarbamate exchange reaction needs to reserve sulfhydryl group; amide In the exchange reaction, the amine exchange reaction of carbamate, vinylamide, and vinyl carbamate requires the retention of an amino group. It should be noted that the nucleophilic group may be exchanged covalently with the binding on the same polymer network/chain or on a different polymer network/chain.

In the present invention, the exchange reaction includes not only the exchange reaction between the above-mentioned exchangeable covalent bonds but also the exchange reaction between different exchangeable covalent bonds. For example, the exchangeable ester bond can generate a thioester bond or an amide bond by exchange reaction with an amino group or a sulfhydryl group; the exchangeable amide bond can generate an ester bond or a thioester bond through exchange reaction with a hydroxyl group or a thiol group; and an exchangeable thiourethane bond; The bond can generate a urethane bond or the like by an exchange reaction with a hydroxyl group. In view of the simplicity and easiness of the implementation, in the embodiment of the present invention, the exchange reaction is preferably an exchange reaction between the same exchangeable covalent bonds, that is, an exchange reaction between the ester bond and the hydroxyl group; The exchange reaction between the thioester bond and the sulfhydryl group is exchanged; the exchange reaction between the amide bond and the amino group is exchanged; the exchange reaction between the vinyl amide bond and the vinyl urethane bond and the amino group is inserted. It should be noted that the carbamate exchange reaction includes both a transesterification reaction and an amine exchange reaction, and can be selectively controlled depending on the hydroxyl group or amino group reserved on the side chain and/or the side chain of the polymer chain. In an embodiment of the invention, the carbamate exchange reaction is preferably a transesterification reaction.

In the present invention, a part of the described exchangeable covalent bond exchange reaction needs to be carried out under catalyst conditions, the catalyst comprising a transesterification reaction (including esters, thioesters, carbonates, carbamates, Catalysts such as thiocarbamates and the like, and amine exchange reactions (including amides, carbamates, thiourethanes, ureas, vinyl amides, vinyl urethanes, etc.). The catalyst is an important component of a dynamic polymer of a hybrid crosslinked network structure provided by the present invention, which can promote the occurrence of a bond exchangeable covalent bond exchange reaction, so that the present invention provides a hybrid The dynamic polymer of the cross-linked network structure has the properties of repeated heating softening and cooling hardening, and is easy to be processed by extrusion, injection, blow molding and welding.

In an embodiment of the present invention, a catalyst for a transesterification reaction (also including a urethane bond) may be selected from the group consisting of: (1) a mineral acid, an organic acid, and an acid salt catalyst thereof. The inorganic acid may, for example, be sulfuric acid, hydrochloric acid, phosphoric acid or the like. The organic acid may, for example, be methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or the like. The salt may, for example, be a sulfate, a hydrogen sulfate, a hydrogen phosphate or the like. (2) The alkali metal of Group IA and the compound thereof may, for example, be lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate or carbonate. (3) The IIA group alkali metal and a compound thereof may, for example, be calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide or magnesium ethoxide. (4) Aluminum metal and a compound thereof, for example, aluminum powder, aluminum oxide, sodium aluminate, a composite of aqueous alumina and sodium hydroxide, and an alkoxy aluminum compound. (5) Tin-based compounds, including inorganic tins and organotins. Examples of the inorganic tins include tin oxide, tin sulfate, stannous oxide, stannous chloride, and the like. The organotins may, for example, be dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tributyltin acetate, tributyltin chloride, and trimethyltin chloride. (6) Group IVB element compound, which may, for example, be titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium oxide, zirconium sulfate, zirconium tungstate, zirconate Tetramethyl ester. (7) An anionic layer column compound whose main component is generally composed of a hydroxide of two metals, which is called a double metal hydroxide LDH, and the calcined product thereof is LDO, and for example, hydrotalcite {Mg ₆ (CO) ₃ ) [Al(OH) ₆ ] ₂ (OH) ₄ · 4H ₂ O}. (8) A supported solid catalyst, for example, KF/CaO, K ₂ CO ₃ /CaO, KF/γ-Al ₂ O ₃ , K ₂ CO ₃ /γ-Al ₂ O ₃ , KF/Mg-La, K ₂ O / activated carbon, K ₂ CO ₃ / coal ash powder, KOH / NaX, KF / MMT (montmorillonite) and other composites. (9) The organozinc compound may, for example, be zinc acetate, zinc acetylacetonate or the like. (10) An organic compound, which may, for example, be 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine Wait. Among them, organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, and 2-MI are preferred; more preferably, TBD and zinc acetate are mixed and coordinated, and 2-MI and zinc acetylacetonate are mixed and coordinated.

In an embodiment of the invention, the catalyst for the amine exchange reaction of an amide, a urethane group, a thiourethane group, a urea group, a vinyl amide or a vinyl carbamate may be selected from the group consisting of: Boric acid, nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine, adjacent Benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N,N'-diphenyl thiourea, bismuth trifluoromethanesulfonate (Sc(OTf) ₃ ), montmorillonite KSF, Neodymium tetrachloride (HfCl ₄ ), Hf ₄ Cl ₅ O ₂₄ H ₂₄ , HfCl ₄ /KSF-polyDMAP, glutamine transaminase (TGase); divalent copper compound, for example, copper acetate; ferric iron The compound may, for example, be an aqueous solution of ferric chloride, an iron sulfate hydrate, an iron nitrate hydrate or the like. Among them, copper acetate is preferred; Sc(OTf) ₃ and HfCl _{4 are} mixed and synergistically catalyzed; HfCl ₄ /KSF-polyDMAP; glycerol, boric acid, and ferric nitrate hydrate are mixed and coordinated.

In embodiments of the invention, certain amide exchange reactions may avoid the use of catalysts, such as the use of microwave radiation. The amine exchange reaction of the urethane group, the thiourethane group or the ureido group can avoid the use of a catalyst, for example, when heated to 160 to 180 ° C, with a pressure of 4 MPa, an amine exchange reaction can take place. The amine exchange reaction of inserting a vinyl amide or a vinyl carbamate can avoid the use of a catalyst which, upon heating above 100 ° C, can undergo an amine exchange reaction by Michael addition. The present invention preferably achieves the exchange reaction by microblogging radiation or heating without the need for additional catalyst addition.

In an embodiment of the present invention, the binding exchangeable covalent bond exists as a polymeric linking point or a crosslinked linking point of a dynamic polymer or as both an aggregated linking point and a crosslinked linking point, forming/maintaining dynamic aggregation a necessary condition for the covalently crosslinked structure, that is, if some or all of the exchangeable covalent bonds are non-regeneratively dissociated, the hybrid crosslinked network dynamic polymer will be dissociated into monomers, polymerized. One or more of the fragment of the chain, the two-dimensional/three-dimensional cluster, that is, the covalently crosslinked network will undergo degradation. In the present invention, unless a specific method is employed to cause non-regenerative dissociation of the bound exchangeable bond, the covalently crosslinked network does not undergo a degradative change, that is, a covalently crosslinked structure is always present. Wherein, it is preferred that the segment between every two covalent cross-linking points in the covalent cross-linking network contains at least one of the bound exchangeable covalent bonds, which is advantageous for the segment to be more fully generated during the bond exchange. Exchange; however, the content can be lower when it is possible to satisfy the non-regenerative dissociation of the bound exchangeable bond resulting in degradation of the covalently crosslinked network. Furthermore, it is not excluded that a bound exchangeable covalent bond is present on a non-covalently crosslinked chain backbone or pendant/side chain/end group. In the present invention, based on the manner in which the bondable exchangeable bond is present, the covalently crosslinked network is a covalently plastic network based on a combined switch mechanism, having glass-like plasticity and self-healing properties.

In an embodiment of the invention, the binding exchangeable covalent bond is selected from the group consisting of an exchangeable ester bond, a carbonate bond, a thioester bond, a dithioester bond, an amide bond, a urethane bond, sulfur a urethane bond, a vinyl amide bond, a vinyl urethane bond, an ethylene thiocarbamate bond, or the like; and a structure represented by the following formulas (1) and (2) At least one of them,

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom.

When X is O or S, R ₁ and R ₂ are absent;

When it is a substituent, the number of carbon atoms of R ₁ , R ₂ and R ₃ is not particularly limited, but the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 10. For the sake of brevity, in the present invention, the range of the number of carbon atoms in the group is indicated in the subscript position of C, indicating the number of carbon atoms of the group, for example, C _1-10 means "having 1 to 10 carbons". atom". C _1-20 means "having 1 to 20 carbon atoms". The "unsaturated C _3-20 hydrocarbyl group" means a compound having an unsaturated bond in a C _3-20 hydrocarbyl group. The "substituted C _1-20 hydrocarbon group" means a compound obtained by substituting a hydrogen atom of a C _1-20 hydrocarbon group. The "hybrid C _1-20 hydrocarbon group" means a compound obtained by substituting a carbon atom in a C _1-20 hydrocarbon group with a hetero atom. In another example, when a group may be selected from a C _1-10 hydrocarbon group, the hydrocarbon group may be selected from any one of the carbon atoms in the range indicated by the subscript, and may be selected from C ₁ , C ₂ , C ₃ , C ₄ , Any one of C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ hydrocarbyl groups. In the present invention, the subscripts marked in the interval form, unless otherwise specified, indicate that any integer within the range may be selected, and the range includes two endpoints.

As the substituent, the structures of R ₁ , R ₂ and R ₃ are not particularly limited and include, but are not limited to, a linear structure, a branched structure containing a pendant 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.

As a substituent, R ₁ , R ₂ and R ₃ may contain a hetero atom or may not contain a hetero atom. The hetero atom described in the present invention is not particularly limited and includes, but not limited to, O, S, N, P, Si, F, Cl, Br, I, B and the like. The number of hetero atoms may be one or two or more. The hetero atom may exist as a substituted atom; it may also exist independently as a divalent linking group, such as -O-(oxy or ether bond), -S-(thio or thioether bond), -N(R)- (Secondary amino group or divalent tertiary amino group) and the like.

R ₁ and R _{2 are} 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 ₁ and R ₂ 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 ₁ and R ₂ are a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _1-20 unsaturated aliphatic hydrocarbon group, an aryl group, an aromatic hydrocarbon group, a C _1-20 heteroalkyl group, a C _1-20 hydrocarbon groupoxy group. Any one or a group of an acyl group, a C _1-20 hydrocarbyl thio acyl group, a C _1-20 hydrocarbylamino acyl group, or a substituted form of any one of the groups. Among them, the acyl group in R ₁ and R ₂ is not particularly limited. The acyl group in R ₁ and R ₂ is more preferably a carbonyl group or a thiocarbonyl group.

More preferably, R ₁ and R ₂ are 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, C _1-20 alkoxy group, aryloxy group, C _1-20 alkylthio group, arylthio group atom or any one group or any one group are substituted form.

Specifically, R ₁ and R _{2 are} selected from, but not limited to, 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. , heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Alkyl, nonadecyl, eicosyl, allyl, propenyl, vinyl, phenyl, methylphenyl, butylphenyl, benzyl, methoxycarbonyl, ethoxycarbonyl, benzene Oxycarbonyl, benzyloxycarbonyl, methylthiocarbonyl, ethylthiocarbonyl, phenylthiocarbonyl, benzylthiocarbonyl, ethylaminocarbonyl, benzylaminocarbonyl, methoxythiocarbonyl, ethoxythiocarbonyl , phenoxythiocarbonyl, benzyloxythiocarbonyl, methylthiocarbonylcarbonyl, ethylthiothiocarbonyl, phenylthiothiocarbonyl, benzylthiothiocarbonyl, ethylaminothiocarbonyl, benzyl Aminothiocarbonyl, substituted C _1-20 alkyl, substituted C _1-20 alkenyl, substituted C _1-20 aliphatic heteroalkyl, substituted heteroaryl, substituted heteroaryl, substituted C _{1- 20} alkoxycarbonyl, substituted aryloxycarbonyl, substituted C _1-20 alkylthiocarbonyl, substituted arylthiocarbonyl substituted C _1-20 alkoxythiocarbonyl, substituted aryl Any one or a group of an oxythiocarbonyl group, a substituted C _1-20 alkylthiothiocarbonyl group, a substituted arylthiothiocarbonyl group, or the like. Among them, butyl includes, but not limited to, n-butyl group and tert-butyl group. Octyl groups include, but are 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.

R ₁ and R _{2 are} preferably a hydrogen atom, a fluorine 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, a decyl group, a decyl group, an undecane group. , dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl Any one or a group of a propylene group, a vinyl group, a phenyl group, a methylphenyl group, a butylphenyl group or a benzyl group.

R _{3 is} selected from a hydrogen atom, a C _1-20 hydrocarbyl group, a C _1-20 heterohydrocarbyl group, a substituted C _1-20 hydrocarbyl group or a substituted heterohydrocarbyl group, or a substituted group of any one of them. form.

More preferably, R ₃ is a hydrogen atom, a C _1-20 alkyl group, a C _1-20 unsaturated aliphatic hydrocarbon group, an aryl group, an aromatic hydrocarbon group, a C _1-20 heteroalkyl group, or any one of the atoms or a group. The replaced form of the regiment.

More preferably, R ₃ is a hydrogen atom, a C _1-20 alkyl group, a C _1-20 alkenyl group, an aromatic hydrocarbon group, a C _1-20 aliphatic hydrocarbon group, a heteroaryl group, a heteroaryl group, or any one of the atoms or groups; A substituted form of any of the groups.

Specifically, R _{3 is} selected from, but not limited to, hydrogen atom, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, eleven Alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl Base, propenyl, vinyl, methylphenyl, butylphenyl, benzyl, substituted C _1-20 alkyl, substituted C _1-20 alkenyl, substituted arene, substituted C _1-20 Any one or a group of a heteroalkyl group, a substituted heteroaryl group or the like.

R _{3 is} further preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, and a decyl group. Alkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, triphenyl Any one or any group of a group, a benzyl group, a methylbenzyl group, a nitrobenzyl group, a C _1-10 halogenated hydrocarbon group, a halogenated benzyl group, a nitrophenyl group, a nitrobenzyl group, or the like The form of being replaced.

More preferably, R ₃ is a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, and a decyl group. Alkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, benzyl, Any one of methylbenzyl and the like.

R _{3 is} most preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, allyl, benzyl, Any one of methylbenzyl and the like.

The binding exchangeable covalent bond group may be selected, for example, from an ester group, a carbonate group, a thioester group, an amide group, a carbamate group, a thiocarbamate group, a urea group, a vinyl amide. a base, a vinyl carbamate group, and a derivative based on the above groups. As an example, the following structure is mentioned, but this invention is not limited to this.

In an embodiment of the present invention, the "covalently crosslinked network skeleton chain" is also a main chain of a three-dimensional infinite network skeleton and a chain skeleton of a crosslinked link. In addition to containing at least one binding exchangeable group on the backbone chain of the covalently crosslinked network, any of the pendant and/or side chains of the backbone chain of the covalently crosslinked network and the non-covalently crosslinked polymer chain The binding exchangeable group may be present at any suitable position such as a position.

In an embodiment of the invention, the supramolecular hydrogen bond crosslinks through a hydrogen bond group ("side hydrogen bond (group))) carried on the pendant and/or side chain of the polymer chain and optionally exists in The hydrogen bond group ("skeletal hydrogen bond (group)") on the polymer chain backbone is realized.

In the present invention, the "polymer chain skeleton" means a non-covalently crosslinked polymer backbone and a group constituting a covalently crosslinked group. Main chains and cross-links on clusters and/or three-dimensional infinite network backbones. The "crosslinking link" may be a covalent bond, an atom, a group, a segment, a cluster, etc., so that the crosslinked link between the polymer chains may also be regarded as a polymer chain skeleton. The "polymer chain side groups and/or side chains" refers to any polymer chain and cross-linking side groups and/or side chains, wherein the side chains also include branches and complexities such as hyperbranched and dendritic chains. Various bifurcation chains in the structure. It is not excluded in the present invention that the hydrogen bonding group on the non-covalently crosslinked polymer chain skeleton participates in the hydrogen bonding crosslinking, and does not exclude hydrogen passing through the non-crosslinked polymer chain side group and/or side chain. The bond group participates in the hydrogen bond crosslinking. Since some of the hydrogen bonds are not directional and selective, the backbone hydrogen bonding groups on the polymer chain backbone can also form hydrogen bonds with the side hydrogen bonding groups on the side chain/side chain of the polymer chain. In the present invention, hydrogen bonding crosslinking in any of the networks may be at any degree of crosslinking, preferably above the gel point where hydrogen bonding is achieved. Since at least one of the covalently crosslinked networks has a cross-linking degree above the gel point of covalent cross-linking, hydrogen bond cross-linking is a supplement to covalent cross-linking regardless of the degree of cross-linking of the hydrogen-bond cross-linking. Dynamic polymers can maintain a balanced structure.

In an embodiment of the present invention, the "hydrogen bond group on the polymer chain skeleton", that is, the "skeletal hydrogen bond group" means that at least a part of the atoms in the group directly participate in the construction of a continuous non-common a polymer backbone or a crosslinked link on a crosslinked polymer backbone or crosslinked network backbone; said "hydrogen bond groups on the pendant and/or side chains of the polymer chain", ie, "side hydrogen bonds" "Group" means that all atoms on the group are on the side group/side chain. The skeleton hydrogen bond group may be formed during polymer polymerization/crosslinking, that is, by forming the hydrogen bond group to cause polymerization/crosslinking; or may be pre-formed and then polymerized/crosslinked; preferably Generated during polymer polymerization/crosslinking. The number of backbone hydrogen bonding groups is generally limited and difficult to control. The side hydrogen bond group may be formed before, after or during the polymerization/crosslinking, and the amount generated before or after may be relatively freely controlled; the linkage structure and length between the side hydrogen bond group and the skeleton chain and The structure itself includes substituents and side groups, etc., which can be diversified to control hydrogen bond strength, steric hindrance, thermal stability, glass transition temperature, etc., thereby regulating dynamic properties and imparting different super toughness to the polymer. Self-healing, stress/strain responsiveness, shape memory and other properties.

In an embodiment of the invention, two or more pendant groups/side chains may be attached to the same atom; the pendant/side chain may continue to have pendant and/or side chains, side groups/side chains The side groups/side chains may continue to have side groups and/or side chains, that is, the side groups/side chains may have a multi-stage chain structure; if not specifically stated, the side groups/side chains may also be star-shaped or ring-shaped, etc. Special structure. The polymer chain of the present invention includes a main chain (backbone chain) and any side chain, and also includes a crosslinked link in a covalently crosslinked network.

The hydrogen bond is composed of a donor (D, that is, a hydrogen atom) of a hydrogen bond group and a receptor (A, that is, an electronegative atom that accepts a hydrogen atom) constitutes a non-covalent bond, and each DA combination is one. Teeth (as shown in the following formula, hydrogen bonding of one, two, and three-tooth hydrogen bonding groups, respectively).

The acceptor of the hydrogen bond group in the present invention preferably contains at least one of the structures represented by the following formula (3).

Wherein A is selected from the group consisting of an oxygen atom and a sulfur atom; and D is selected from a nitrogen atom and a CR group. Wherein R is selected from a hydrogen atom, a substituted atom, and a substituent. In the present invention, A is preferably an oxygen atom, and D is preferably a CR group.

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.

When it is a substituent, the structure of R is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a side group, or a cyclic structure, and a linear structure is preferable. 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 is 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 is selected from, but not limited to, 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, Octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, ten Nonaalkyl, eicosyl, allyl, propenyl, vinyl, phenyl, methylphenyl, butylphenyl, benzyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, Benzyloxycarbonyl, methylthiocarbonyl, ethylthiocarbonyl, phenylthiocarbonyl, benzylthiocarbonyl, ethylaminocarbonyl, benzylaminocarbonyl, methoxythiocarbonyl, ethoxythiocarbonyl, phenoxy Thiocarbonyl, 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 alkane Any one or a group of an oxythiocarbonyl group, a substituted aryloxythiocarbonyl group, a substituted C _1-20 alkylthiothiocarbonyl group, a substituted arylthiothiocarbonyl group, and the like. Among them, butyl includes, but not limited to, n-butyl group and tert-butyl group. Octyl groups include, but are 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 donor of the hydrogen bond group in the present invention preferably contains a structure represented by the following formula (4).

The structures represented by the general formulae (3) and (4) may be a side group, an end group, a linear structure, a branched structure containing a side group, or a ring structure or the like. 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 pendant hydrogen bond groups carried on the pendant and/or side chains contain both structural units of the formulae (3) and (4). In an embodiment of the invention, it is preferred that the pendant hydrogen bonding group form a hydrogen bond of no more than four teeth. Since the more the number of teeth, the stronger the hydrogen bonding effect, and generally does not exceed the hydrogen bond of the four teeth, especially the hydrogen bond of not more than three teeth, the dynamics are better, and the side group/side chain of the present invention can effectively provide sufficient dynamics. Hydrogen bonding crosslinks. According to an implementation effect of the present invention, the side hydrogen bond group is preferably selected from the group consisting of an amide group, a carbamate group, a thiocarbamate group, a urea group, a pyrazole, an imidazole, an imidazoline, a triazole, an anthracene, a porphyrin, and Their derivatives.

As an example, the side hydrogen bond group may have the following structure, but the present invention is not limited thereto.

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 the present invention, more than one of the above-mentioned side hydrogen bond groups may be contained in the same polymer, and more than one of the above-described side hydrogen bond groups may be contained in the same network. The compound to which the side hydrogen bond group can be introduced is not particularly limited, and the type and mode of the reaction for forming the group are not particularly limited. The reaction of isocyanate with an amino group, a hydroxyl group, a mercapto group or a carboxyl group, and the reaction of a succinimide ester with an amino group, a hydroxyl group, and a mercapto group are preferred.

In the present invention, the side hydrogen bond group can form a hydrogen bond crosslink more efficiently than a hydroxyl group, a mercapto group or an amino side group for a bond exchangeable reaction, and can be adjusted by hydrogen bond acceptor and The number of donors controls the number of teeth and the strength/dynamics of hydrogen bonds; based on the simultaneous presence of acceptors and amino donors, the hydrogen bonds formed are more environmentally responsive; the hydrogen bonds formed are also capable of The glass transition temperature of the material has more effects, in particular by adjusting the number of teeth of the hydrogen bond, the size of the bond, the length and flexibility of the link to the polymer chain, and the like.

In an embodiment of the present invention, in addition to the above-mentioned side hydrogen bond group, other side hydrogen bond groups may be selectively contained. These include, but are not limited to, carboxyl groups, fluorine groups, and the like. It should be noted that when hydroxyl, amino, sulfhydryl groups are present, they are also additional optional pendant hydrogen bonding groups in the present invention. These optional/additional other pendant hydrogen bonding groups can be used to adjust the strength and dynamics of hydrogen bonding under suitable conditions.

In an embodiment of the present invention, the skeleton hydrogen bond group may be a hydrogen bond group capable of forming an arbitrary number of teeth; a hydrogen bond group has both a hydrogen bond acceptor and a hydrogen bond donor; or may be a partial hydrogen The bond group contains a hydrogen bond donor, and the other part of the hydrogen bond group contains a hydrogen bond acceptor; preferably, both the acceptor and the donor are contained.

In the embodiment of the present invention, the optional skeleton hydrogen bond group present on the polymer chain skeleton may be exemplified by the following structure, but the present invention is not limited thereto.

In one embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network has only one network (the first network structure), characterized in that the covalent cross-linking in the network reaches above the covalent gel point; Wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming/maintaining a covalent crosslinked structure of the dynamic polymer; a pendant group of the polymer chain backbone and/or The side hydrogen bond group is present on the side chain. The polymer is above the gel point Covalent cross-linking to maintain a balanced structure provides supramolecular hydrogen bonding crosslinks by hydrogen bonding between the side hydrogen bonding groups. In this embodiment, covalent cross-linking containing a bound exchangeable covalent bond is used to provide a balanced structure in which exchangeable covalent bonds provide covalent dynamics; hydrogen bonding by the formation of pendant hydrogen bonding groups provides additional Crosslinking and supramolecular dynamics.

In another embodiment of the present invention, the dynamic polymer of the hybrid cross-linking network is composed of two networks (fourth network structure), characterized in that the first network is the first network structure; The second network does not contain covalent crosslinks, but side hydrogen groups are present on the side groups and/or side chains of the polymer chain; the side hydrogen bond groups between the first network and the second network can form hydrogen with each other. key. In the network structure, the covalent crosslinks are maintained by the covalent cross-linking in the first network, and the covalent bonds exchanged therein provide covalent dynamics; the cross-linking through the first and second networks provides super Molecular dynamics.

When the side hydrogen bonding group is present in the covalently crosslinked network, in principle, the number and distribution of the side hydrogen bonding groups on the polymer segment between the two covalent crosslinking points are not limited, and Is the segment between any two covalent cross-linking points The side hydrogen bond group may also be a side hydrogen bond group on the segment between the partial crosslink points; on the segment between the covalent crosslinks containing the side hydrogen bond group, preferably Each segment contains not less than 2 of said side hydrogen bond groups, more preferably each segment contains not less than 5 of said side hydrogen bond groups; said side hydrogen bond group is covalently distributed throughout The number in the network is also not limited, and it is preferable that the segment between each of the two covalent crosslinking points contains not less than 0.1 of the side hydrogen bond groups, and more preferably contains not less than 1 One of the side hydrogen bonding groups.

In the embodiments of the present invention, covalent crosslinking may take any suitable reaction, including but not limited to the following types: reaction of isocyanate with amino group, hydroxyl group, mercapto group, carboxyl group, epoxy group, carboxylic acid, acid halide, acid anhydride, activity Reaction of ester with amino group, hydroxyl group, sulfhydryl group, acrylate radical reaction, acrylamide radical reaction, double bond radical reaction, reaction of epoxy group with carboxylic acid, amino group, hydroxyl group, sulfhydryl group, phenolic reaction, azide-alkyne Click reaction, thiol-double bond/alkyne click reaction, tetrazine-norbornene reaction, silanol condensation reaction; preferably reaction of isocyanate with amino group, hydroxyl group, sulfhydryl group, reaction of acid halide, acid anhydride with amino group, hydroxyl group, sulfhydryl group, acrylic acid Ester free radical reaction, acrylamide free radical reaction, double bond free radical reaction, reaction of epoxy with carboxylic acid, amino group, hydroxyl group, sulfhydryl group. In any network structure, covalent cross-linking may have one or more types of reactions, means of reaction, and structure. Preferably, the reaction temperature does not exceed 100 ° C, more preferably does not exceed 60 ° C, more preferably does not exceed 25 ° C, and most preferably does not require a heating reaction, such a reaction process is simple, fast, and flexible.

The formation or introduction of a binding exchangeable covalent bond group for forming a reversible dynamic crosslink in the present invention can be carried out before, after or during covalent crosslinking. The exchangeable covalent bond group is selected, for example, from an ester group, a carbonate group, an amide group, a carbamate group, a thiocarbamate group, a urea group, a vinyl amide group, a vinyl urethane group. And derivatives based on the above groups. The formation or introduction may be carried out by any suitable reaction, including but not limited to the following types: reaction of a carboxyl group with an epoxy group, a hydroxyl group, a mercapto group, an amino group, an acid halide, an acid anhydride, a reaction of an active ester with a hydroxyl group, a mercapto group, an amino group, an isocyanate and an amino group. The reaction of a hydroxy group, a thiol group, a carboxyl group, a ketone, an aldehyde, and a primary amine.

In an embodiment of the present invention, preferably, the bondable exchangeable ester bond is formed by reacting a polyvalent carboxylic acid, a polybasic acid halide, a polybasic acid anhydride, and/or a polyvalent active ester compound with a polyhydroxy compound; The acid compound is formed by polycondensation reaction; it can also be formed by reacting a polyvalent carboxylic acid with a polyvalent epoxy compound. Among them, a reaction of a polyvalent carboxylic acid and/or a polybasic acid halide compound with a polyhydroxy compound, a self-polycondensation reaction of a hydroxy group-containing carboxylic acid compound, a reaction of a polyvalent carboxylic acid with a polyvalent epoxy compound, and a polybasic acid halide are more preferable. The reaction of a compound with a polyhydroxy compound, the reaction of a polyvalent carboxylic acid with a polyvalent epoxy compound; most preferably the reaction of a polyvalent carboxylic acid with a polyvalent epoxy compound. It should be noted that in order to cause the transesterification reaction to occur, the crosslinked network obtained after covalent crosslinking must contain a hydroxyl group, preferably having a hydroxyl group on the side chain and/or the side chain of the covalently crosslinked network backbone polymer chain. . Therefore, the above polyhydroxy compound preferably has at least one polyhydroxy compound having three or more hydroxyl groups; and the above hydroxyl group-containing carboxylic acid compound preferably has at least one carboxylic acid compound having two or more hydroxyl groups. If the polyepoxide is involved in the reaction, there is no such limitation.

In an embodiment of the present invention, preferably, the bondable exchangeable thioester bond is formed by reacting a polyvalent carboxylic acid, a polybasic acid halide, a polybasic acid anhydride, and/or a polyvalent active ester compound with a polyfluorenyl compound; The carboxylic acid compound is formed by polycondensation. Among them, a polycondensation reaction of a polycarboxylic acid and/or a polybasic acid halide compound and/or a polyvalent active ester compound with a polyfluorenyl compound, a polycondensation reaction of a mercapto group-containing carboxylic acid compound, and more preferably a polybasic acid halide compound and/or The reaction of a polyvalent active ester compound with a polyfluorenyl compound. It is to be noted that in order to cause the occurrence of the thioester exchange reaction, it is preferred that the crosslinked network obtained after covalent crosslinking has a mercapto group on the side chain and/or the side chain of the polymer chain. Therefore, the above polyfluorenyl compound preferably has at least one polyfluorenyl compound having 3 or more mercapto groups. The thiol group-containing carboxylic acid compound preferably has at least one carboxylic acid compound having two or more mercapto groups.

In an embodiment of the present invention, it is preferred that the bondable exchangeable amide bond is formed by reacting a polyvalent carboxylic acid, a polybasic acid halide, a polybasic acid anhydride, and/or a polyvalent active ester compound with a polyamine compound; The acid compound is obtained by polycondensation reaction; it can also be formed by reacting a carboxylic acid with an isocyanate; wherein, more preferably, a reaction of a polyvalent carboxylic acid and/or a polybasic acid halide compound and/or a polyvalent active ester compound with a polyamine compound, with an amino group The self-polycondensation reaction of the carboxylic acid compound; more preferably, the reaction of the polybasic acid halide compound and/or the polyvalent active ester compound with the polyamine compound is employed. It should be noted that in order to cause the occurrence of the amide exchange reaction, it is preferred that the crosslinked network obtained after covalent crosslinking must have a side chain and/or a side chain of the polymer chain. With an amino group. Therefore, the above polyamine compound preferably has at least one polyamine compound having three or more amino groups.

In an embodiment of the present invention, preferably, the bondable exchangeable urethane bond is formed by reacting a polyol compound and a polyisocyanate compound; or may be formed by reacting a polyvalent carbonate with a polyamine compound; The formate compound is reacted with a polyamine compound; among them, a reaction of a polyol compound and a polyisocyanate compound is more preferably used. It should be noted that in order to cause the occurrence of the carbamate exchange reaction, it is preferred that the crosslinked network obtained after covalent crosslinking has an amino group on the side chain and/or the side chain of the polymer chain. Therefore, the above polyol compound preferably has at least one polyol compound having one or more amino groups on its side group and/or side chain; the above polyamine compound preferably has at least one polyamine having three or more amino groups. Compound.

In an embodiment of the present invention, it is preferred that the bondable exchangeable thiourethane bond is formed by reacting a polythiol compound and a polyisocyanate compound; or reacting a polyisothiocyanate compound with a polyol compound. Among them, a reaction of a polyvalent thiol compound and a polyisocyanate compound is more preferably used. In addition, in order to cause an amine exchange reaction of a thiocarbamate, it is preferable to carry an amino group in a side chain and/or a side chain of a polymer chain in the crosslinked network obtained after covalent crosslinking. Therefore, the above polythiol compound preferably has at least one polythiol compound having one or more amino groups in its side group and/or side chain.

In an embodiment of the invention, it is preferred that the ureido group is formed by reacting a polyamine compound and a polyisocyanate compound; or it may be formed by reacting a polyvalent carbamoyl chloride with a polyamine compound. Among them, a reaction of a polyamine compound and a polyisocyanate compound is more preferably used. It should be noted that in order to cause the urea exchange reaction to occur, it is preferred that the crosslinked network obtained after covalent crosslinking has an amino group on the side chain and/or the side chain of the polymer chain. Therefore, the above polyamine compound preferably has at least one polyamine compound having three or more amino groups.

In an embodiment of the present invention, it is preferred that the bondable exchangeable vinyl amide group or the vinyl urethane group is formed by reacting a corresponding polyhydric ketone, a polyvalent aldehyde, and a polyamine compound. Among them, it is more preferred to use a corresponding reaction of a polyvalent aldehyde with a polyamine compound. Wherein, the corresponding polybasic ketone and polyvalent aldehyde conform to the structure of the formula (5). Wherein, the general formula includes, but is not limited to, a linear structure, a branched structure containing a side group, or a cyclic structure. It should be noted that in order to cause the occurrence of an amine exchange reaction of inserting a vinyl amide or a vinyl carbamate, it is preferred that the crosslinked network obtained after covalent crosslinking has a side chain and/or a side chain of the polymer chain. Amino group. Therefore, the above polyamine compound preferably has at least one polyamine compound having three or more amino groups.

In the present invention, preferred polycarboxylic acids for the preparation of the bound exchangeable ester group include small molecules, oligomers and high molecular polycarboxylic acids. The group to which a plurality of carboxyl groups are bonded is not particularly limited. For example, an organic acid having a saturated or unsaturated hydrocarbon group may be mentioned, and the hydrocarbon group may be any of an aliphatic group, an alicyclic group, and an aromatic group.

Specific examples of the carboxylic acid include malonic acid, maleic acid, succinic acid, oxaloacetic acid, dimethylmalonic acid, isopropylmalonic acid, benzylmalonic acid, and 1,1-epoxy. Dicarboxylic acid, 1,1-cyclobutyl dicarboxylic acid, dibutylmalonic acid, ethyl (1-methylpropyl)malonic acid, ethyl (1-methylbutyl)malonic acid , ethyl (isoamyl)malonic acid, phenylmalonic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-oxoglutaric acid, 3-oxoglutaric acid, 5 -norbornene-endo-2,3-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedioic acid, pyrrolidine-3,4- Dicarboxylic acid, camphoric acid, chloric acid, cyclic acid, 5-methylisophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 4-methyl-1,2-benzenedicarboxylate Acid, 4-chlorophthalic acid, 3,4-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,6- Pyridine dicarboxylic acid, 2,4-dimethylpyrrole-3,5-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, 5-methylpyridine-2,3-dicarboxylic acid, 5-ethyl Pyridine-2,3-dicarboxylic acid, 5-methoxymethyl-2,3-pyridinedicarboxylic acid, 4,5-pyridazinedicarboxylic acid, 2,3-pyrazinedicarboxylic acid , 5-methylpyrazine-2,3-dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 2-propylimidazolium dicarboxylic acid, 2-propylimidazolium dicarboxylic acid, diphenyl phthalate, 4, 4'-stilbene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 2,2'-bipyridyl-5,5'-dicarboxylic acid, 2,2 '-Bipyridyl-3,3'-dicarboxylic acid, 4-pyrone-2,6-dicarboxylic acid, catechol-O, O'-diacetic acid, thiophene-2,3-dicarboxylic acid , 2,5-thiophene dicarboxylic acid, 2,5-dicarboxylic acid-3,4-ethylenedioxythiophene, 1,3-propane Ketodicarboxylic acid, methylene succinic acid, 2-methyl-2-butenedioic acid (citraconic acid and mesaconic acid), 1,3-butadiene-1,4-dicarboxylic acid, butyl Alkynedioic acid, norbornene-2,3-dicarboxylic acid (bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid), bicyclo[2.2.1]hept-2-ene-2 , 3-dicarboxylic acid, diglycolic acid, dithiol dihydroxyacetic acid, malic acid, tartaric acid, 2,3-dimercaptosuccinic acid, 2,3-dibromosuccinic acid, pyrazole oxalic acid, 4 , 4'-Dichloro-2,2'-dicarboxybiphenyl, 4,4'-dibromo-2,2'-dicarboxybiphenyl, gluconic acid, sucrose, pamoate, 2-bromo Succinic acid, 2-mercaptosuccinic acid, 1,3-adamantane dicarboxylic acid, 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylic acid, carbonylmalonic acid, Ethoxymethylenemalonic acid, 3,3'-dithiodipropionic acid, acetylmalonic acid, and the like. The above structures include various isomeric forms such as cis, trans, D, and L, such as malic acid including D type and L type.

As the acid halide, the acid halide can be obtained by reacting a carboxylic acid with an acid halide of a mineral acid such as phosphorus trichloride, phosphorus pentachloride or thionyl chloride. Among them, a halogen atom is preferably a chlorine or a bromine atom. Specific examples of the diacid halide compound include oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, fumaric acid chloride, diethylene glycol bischloroformate, phthaloyl chloride, and the like. Phthalic acid chloride, terephthaloyl chloride, 3,6-endomethyl-1,2,3,6-tetrahydrophthaloyl chloride, oxalyl bromide. Specific examples of the disulfonyl chloride compound include 4,4'-oxybisbenzenesulfonyl chloride and methyl dichlorosulfonate.

Specific examples of the acid anhydride include propionic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, benzoic anhydride, benzoic anhydride, 4-methylhexahydrophthalic anhydride, and 2 , 2-dimethylsuccinic anhydride, cyclopentane-1,1-diacetic anhydride, 1,1-cyclohexyldiacetic anhydride, 2-methylene succinic anhydride, caroic anhydride, cyclobutane-1, 2-Dicarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 1,2,5,6-tetrahydrophthalic anhydride, 3- Methyltetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 2,3-dichloromaleic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 3-methylphthalic anhydride, 4-tert-butylphthalic anhydride, 1,8-naphthalic anhydride, 2,2'-diphthalic anhydride, 4-fluoro-o-benzene Dicarboxylic anhydride, 3-fluorophthalic anhydride, 4-bromophthalic anhydride, 4-chlorophthalic anhydride, 3,6-dichlorophthalic anhydride, 3-nitro-o-phenylene Formic anhydride, 4-nitrophthalic anhydride, 4-bromo-1,8-naphthalic anhydride, 4,5-dichloro-1,8-naphthalic anhydride, 4-nitro-1,8 -naphthalic anhydride, Anhydride, norbornene anhydride, methyl endomethylene tetrahydrophthalic anhydride methyl, isatoic anhydride, 2,3-pyridinedicarboxylic acid anhydride, 2,3-pyrazinedicarboxylic anhydride, benzothioxanthene dicarboxylic anhydride and the like.

Specific examples of the active ester include oxalate, malonate, methylmalonate, ethylmalonate, butylmalonate, succinate, and 2-methylbutylate. Diester, 2,2-dimethylsuccinate, 2-ethyl-2-methyl-succinate, 2,3-dimethylsuccinate, glutarate, 2- Methylglutarate, 3-methylglutarate, 2,2-dimethylglutarate, 2,3-dimethylglutarate, 3,3-dimethylglutaric acid Aliphatic acid of ester, adipate, pimelate, suberate, sebacate, sebacate, maleate, fumarate, peptide acid ester, polyamino acid ester, etc. Ester, especially its succinimide ester; aromatic acid of phthalate, isophthalate, terephthalate, m-aminobenzoate, methylparaben, etc. The ester, especially its succinimide ester.

In the present invention, preferred polyol compounds for the preparation of bound exchangeable ester groups include small molecules, oligomers and high molecular polyols. The group to which a plurality of alcohol units are bonded is not particularly limited.

In the embodiment of the present invention, as specific examples thereof, small molecule polyols include, but not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, and diethylene glycol. Glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, heptanediol, Octanediol, decanediol, decanediol, trimethylolpropane, glycerin, pentaerythritol, xylitol, mannitol, sorbitol, sucrose, liquid crystal polyol, and the like.

In the embodiment of the present invention, as specific examples thereof, oligomers and polymer polyols include, but are not limited to, polyester polyols, polyether polyols, polyolefin polyols, polycarbonate polyols, poly Other polymer polyols such as silicone polyols, polysulfone polyols, vegetable oil polyols and biopolyester polyols, liquid crystal polyols, and the like, also include copolymers and modified forms thereof. The oligomer and the polymer polyol can be synthesized by a well-known polymerization method, and can also be subjected to copper-catalyzed azide-alkyne addition, mercapto-ene addition, mercapto-alkyne addition, tetrazine-norbornene. The reaction is prepared by addition or condensation reaction.

As the polyester polyol, it may be obtained by condensing (or transesterifying) an organic dicarboxylic acid (anhydride or ester) with a polyhydric alcohol (including a glycol) or by polymerizing a lactone and a polyhydric alcohol. The dibasic acid is phthalic acid or phthalic anhydride or an ester thereof, adipic acid, halogenated phthalic acid or the like. The polyhydric alcohol is ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, 1,4-butanediol or the like.

As the polyether polyol, it is obtained by addition polymerization of an active hydrogen group-containing compound and an epoxide in the presence of a catalyst. Examples of the active hydrogen group-containing compound include propylene glycol, glycerin, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylenediamine, sorbitol, sucrose, bisphenol A, bisphenol S, and trisole. (2-hydroxyethyl) isocyanate, toluenediamine, and the like. Examples of the epoxide include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), epichlorohydrin (ECH), and tetrahydrofuran (THF).

As the polyolefin polyol, for example, a terminal hydroxyl group polyethylene, a terminal hydroxyl group polypropylene, a polybutadiene polyol, a hydroxyl group polybutadiene-acrylonitrile, a hydroxyl terminated styrene butadiene liquid rubber, a hydrogenated hydroxyl group polybutadiene can be cited. Alkene, hydroxyl terminated polyisoprene, hydrogenated hydroxyl terminated polyisoprene, polystyrene-allyl alcohol copolymer polyol, and the like.

As the polycarbonate polyol, a small molecule diol and a small molecule carbonate are generally used for transesterification in the presence of a catalyst, and finally, a small molecule is extracted under reduced pressure to obtain a polycarbonate diol. Examples of the small molecule diol include 1,6-hexanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,5-pentanediol, and 3-methylpentane. Alcohol, etc. Examples of the small molecule carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

The polyorganosiloxane is a polymer compound in which Si-O-Si is a main chain and an organic group is bonded to a Si atom. Its structural formula is: (R _n SO _(4-n)/2 ) _m . Wherein R is an organic group such as a methyl group, an ethyl group, a phenyl group, a vinyl group or the like; n is the number of organic groups attached to the silicon atom (1 to 3); and m is a degree of polymerization. The polyorganopolyhydric alcohol may, for example, be hydrolyzed by dichlorosilane to form silanol, and then dehydrated and polycondensed to obtain a hydroxyl-terminated linear polyorganodiol. For the purposes of the present invention, the selected polyorganopolyhydric alcohol may be a hydroxyl terminated polyorganosiloxane, or a polyorganosiloxane having a hydroxyl group at a pendant group, or a polyorganosiloxane having a hydroxyalkyl group at the terminal or pendant group. Oxytomane.

The polysulfone is a polymer compound having a hydrocarbon group-SO ₂ -hydrocarbyl chain link in the main chain of the molecule. The polysulfone is generally an aromatic polymer obtained by polymerizing a dialkali metal salt of an aromatic dihydroxy compound and a living aromatic dihalide. The aromatic dihydroxy compound may, for example, be bisphenol A, bisphenol S or 4,4'-dihydroxybiphenyl. The living aromatic dihalide may, for example, be terephthaloyl chloride or 4,4-dichlorodiphenyl sulfone. For the purposes of the present invention, the polysulfone polyol selected may be a hydroxyl terminated polysulfone or a polysulfone having a hydroxyl group at the pendant group.

Examples of the vegetable oil polyol include castor oil, castor oil derivative polyol, soybean oil polyol, palm oil polyol, and the like. For the purposes of the present invention, the selected vegetable oil polyols are primarily used as raw materials for polyurethane rigid foam materials.

The polymer polyol may, for example, be a styrene-acrylonitrile graft polyether polyol based on PO-EO copolyether triol, abbreviated as POP. A polymer having a plurality of hydroxyl groups in its side group may also be used, and examples thereof include polyvinyl alcohol and polyhydroxyethyl acrylate.

Examples thereof include polyethylene glycol, polytrimethylene ether glycol, polytetrahydrofuran, polyoxypropylene diol, polyoxypropylene triol, bisphenol A polyoxyethylene ether, and polyethylene glycol diphthalate. Glycol, polybutadiene polyol, hydroxyl-terminated polybutadiene-acrylonitrile, polydimethylsilyl polyol, polyarylsulfone polyol, castor oil polyol, polyvinyl alcohol, polyhydroxyethyl acrylate, benzene The chemical structural formula of the ethylene-acrylonitrile grafted polyether polyol is as follows:

In an embodiment of the present invention, a preferred polyvalent epoxy compound for preparing the bound exchangeable ester group may be selected from the group consisting of a binary epoxy compound and a ternary or higher epoxy compound. Examples of the binary epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydroquinone diglycidyl ether, and ethylene glycol diglycidyl ether. Ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly 1 , 4-butanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether , diglycidyl terephthalate, epoxidized polyunsaturated fatty acid and epoxidized limonene. Examples of the polyvalent epoxide containing at least three epoxy functional groups include castor oil triglycidyl ether, 1,1,1-tris(hydroxymethyl)propane triglycidyl ether, trisphenol triglycidyl ether, and glycerin. Triglycidyl ether, glyceryl propoxy triglycidyl ether, glyceryl ethoxy triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol Glycidyl ether, poly(glycidyl acrylate), polyglycidyl methacrylate, epoxidized polyunsaturated fatty acid, epoxidized vegetable oil, epoxidized fish oil, and the like.

As an example, 1,2,7,8-diepoxyoctane, 1,3-diglycidyl ether glycerol, neopentyl glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl 3 can be mentioned. , 4-epoxycyclohexylformate, bisphenol A diglycidyl ether, 2,2'-[1,4-phenylenebis(oxymethylene)]dioxirane, 1,1,3 ,3-tetramethyl-1,3 bis[3-(oxiranylmethoxy)propyl]disiloxane, 1,1,1-tris(hydroxymethyl)propane triglycidyl ether, N , N-diglycidyl-4-glycidoxyaniline, pentaerythritol polyglycidyl ether, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, poly The chemical structure of (glycidyl acrylate) and polyglycidyl methacrylate is as follows:

In an embodiment of the present invention, preferred for preparing the bound exchangeable amide group, urea group, vinylidene group, A vinyl carbamate-based polyamine compound, including but not limited to small molecule polyamines, oligomers, and polymeric polyamines. The molecular weight, the skeleton and the like are not particularly limited as long as they are compounds having two or more amino groups, and examples thereof include, but are not limited to, aromatic polyamines and aliphatic polyamines shown below.

Specific examples of the small molecule aromatic polyamine include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, m-phenylenediamine, tris(dimethylaminomethyl)phenol, and Aminodiphenylmethane, 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 3,5-dimethylthiotoluenediamine (DMTDA), 3,5-diethyl Toluene diamine (DETDA).

Specific examples of the small molecule aliphatic polyamine include methylene diamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentane. Amine, 1,6-hexanediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, diaminododecane, diaminotetradecane, diaminooctadecane, Diethylenetriamine, triethylenetetramine, N-(6-aminohexyl)-1,6-hexanediamine, 1,3-cyclopentanediamine, 1,7-heptanediamine, 5- Methyl decane-1,9-diamine, diaminocyclohexane, 4,4'-diaminobiscyclohexylmethane, oct-4-ene-1,8-diamine, 1,2-diphenyl Diamine, 2-phenyl-1,2-butanediamine, 3-phenyl-1,2-propanediamine, 3-oxa-1,5-pentanediamine, 1,8-diamine- 3,6-dithiaoctane, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, 1,3,5-tris(aminomethyl)-2,4,6-tri Ethylbenzene, undecane-1,6,11-triamine, N-(2,3-diaminopropyl)-1,2,3-propanetriamine, N,N,N,N-tetra 3-aminopropyl)-1,4-butanediamine and the like.

As oligomers and polymeric polyamines, they may include, but are not limited to, polyamines based on polyesters, polyethers, polyolefins, polycarbonates, polyorganosilicones, vegetable oils, and other polymers, and the like. Specifically, for example, a copolyether diamine, a terminal amino polyether having an aromatic amino group at the end, and an amino terminated dimethyl silicone oil can be exemplified. Its chemical structure is as follows,

In an embodiment of the invention, preferred are the polyvalent mercapto compounds used to prepare the bound exchangeable thiocarbamate groups, including but not limited to small molecule polyfluorenyl groups, oligomers, and polymeric polythiol compounds. The compound having two or more thiol groups is not particularly limited as long as it has a compound having two or more thiol groups, and specific examples thereof include, but are not limited to, the compounds shown below.

Specific examples of the small molecule polyvalent fluorenyl compound include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2-butanedithiol, and 1 , 3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-anthracene Mercaptan, 2,3-butanedithiol, biguanide ethyl sulfide, 3,7-dithia-1,9-nonanedithiol, 3-mercapto-β-4-dimethylcyclohexyl Mercaptan, 1,4-benzenedithiol, phthalic acid, 3,4-toluene dithiol, 1,5-naphthalene dithiol, lutidine dithiol, 4,4'-dimercapto Phenyl sulfide, dimercapto-3,6-dioxooctane, 1,5-mercapto-3-thiopentane, 1,3,5-triazine-2,4,6-trithiol, 2- Di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris(β-thiopropionate), trimethylolpropane tris(thioglycolate), and the like.

As the oligomer and the polymer polyvalent mercapto compound, it may include, but is not limited to, a polythiol based on polyester, polyether, polyolefin, polycarbonate, polyorganosilicon, vegetable oil, and other polymers, and the like.

In an embodiment of the invention, preferred isocyanate compounds for preparing the bound exchangeable carbamate, thiocarbamate, ureido groups include, but are not limited to, small molecules, oligomers, and Molecular polyisocyanate compound. The compound having two or more isocyanates is not particularly limited as long as it is a compound having two or more isocyanates, and specific examples thereof include, but are not limited to, the compounds shown below.

As small molecular isocyanates, including but not limited to, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), polymethylene polyphenyl isocyanate (PAPI), liquefied MDI, dicyclohexylmethane diisocyanate (HMDI), naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), phenylenediethylene diisocyanate (XDI), dimethylbiphenyl diisocyanate (TODI), 1,4-cyclohexane diisocyanate (CHDI), four M-m-xylylene dimethylene diisocyanate (m-TMXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), cyclohexane dimethylene diisocyanate (HXDI), norbornane Diisocyanate (NBDI), TDI dimer, triphenylmethane triisocyanate (TTI), 4,4',4"-triphenyl triisocyanate (TPTI), HDI trimer, IPDI trimer , TDI trimer, MDI trimer, TDI-TMP adduct, and the like.

As oligomeric and polymeric isocyanate compounds, including, but not limited to, polyisocyanate compounds based on polyesters, polyethers, polyolefins, polycarbonates, polyorganosilicones, vegetable oils, and other polymers, and the like.

In the embodiments of the present invention, some small molecules containing two or more different functional groups are also allowed as raw materials. Typical such as amino acids or derivatives thereof, such as glycine, tyrosine, fabasutoside, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamine Amino acids such as acid, cysteine, methionine, proline, N-(p-aminobenzoyl)-β-alanine, preferably neutral amino acids such as glycine, alanine, and β-alanine, and derivatives thereof a combination of a hydroxyl group, a thiol group, and an amino group, including but not limited to: 2-mercaptoethanol, aminoethylethanolamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylidene)ethanol, 1- Amino-2-propanol, 4-hydroxyphenethylamine; primary amine containing 2 hydroxyl groups, including but not limited to 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol , N,N-bis(2-hydroxyethyl)ethylenediamine, 3-amino-1,2-propanediol, 2-amino-1-[4-(methylthio)phenyl]-1,3-propanediol , 2-amino-1-phenyl-1,3-propanediol, 2-(3,4-dihydroxyphenyl)ethylamine, 2-amino-1,3-benzenediol, etc.; hydroxycarboxylic acid, including but Not limited to 2-hydroxypropionic acid, 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2- Base acid, 2-hydroxydecanoic acid, 2-hydroxyundecanoic acid, 2-hydroxylauric acid, salicylic acid, 2-phenyl-3-hydroxypropionic acid, mandelic acid, 2,2-diphenyl- 2-hydroxyacetic acid, 3-phenyl-2-hydroxypropionic acid, 2-phenyl-2-methyl-2-hydroxyacetic acid, etc.; carboxylic acid (dihydroxymonocarboxylic acid) containing two hydroxyl groups, including but not Limited to 2,3-dihydroxypropionic acid, 2,2-dimethylolpropionic acid, 2,4-dihydroxy-3,3-dimethylbutyric acid, N,N-dihydroxyethylglycine, 2, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzene Formic acid, 3,4-dihydroxyphenylacetic acid, 3,5-dihydroxyphenylacetic acid, 3,4-dihydroxycinnamic acid, 2,6-dihydroxypyridine-4-carboxylic acid, 4,8-dihydroxyquinoline -2-carboxylic acid.

The above polycarboxylic acid, polybasic acid halide, polybasic acid anhydride, polyvalent active ester, polyhydric alcohol, polyvalent epoxy, polyamine, polydecyl group, polyisocyanate compound and small molecules having two or more different functional groups may be used alone. One of them or two or more of them can be used in combination. A mixture of two or more kinds may be used in combination, and the use of a dynamic polymer (or composition) having a hybrid crosslinked network according to the present invention, and a hybrid cross-linking of the present invention The physical properties required for the dynamic polymer (or composition) of the network are adjusted in an appropriate ratio.

The formation or introduction of a hydrogen bond group for forming a supramolecular crosslink in the present invention can be carried out before, after or during covalent crosslinking. It is preferably carried out before or during the crosslinking, more preferably before the crosslinking. Because it is carried out after covalent cross-linking, it is generally necessary to add the relevant reagent by swelling, and the process is complicated and the effect is poor.

In the embodiment of the present invention, the formation or introduction of a hydrogen bond group may employ any suitable reaction, including but not limited to the following types: reaction of an isocyanate with an amino group, a hydroxyl group, a thiol group, a carboxyl group, an acrylate radical reaction, and a double bond free Base reaction, double bond cyclization reaction, reaction of epoxy with amino group, hydroxyl group, sulfhydryl group, carboxyl group, azide-alkyne click reaction, thiol-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine - norbornene reaction, reaction of active ester with amino group, hydroxyl group, sulfhydryl group, silanol condensation reaction; reaction of isocyanate with amino group, hydroxyl group, sulfhydryl group, reaction of urea-amine, amidation reaction, active ester with amino group, hydroxyl group, The reaction of sulfhydryl. In any of the network structures, the supramolecular crosslinking of the side groups/side chains may have one or more types of reactions, reaction means, and structures.

Embodiments of the partial preparation method of the network structure of the present invention are exemplified below.

In the first network structure of the present invention, the dynamic polymer of the hybrid crosslinked network has only one network, and the covalent cross-linking in the network reaches above the gel point; wherein the covalent cross-linking contains at least one The bound exchangeable covalent bond is crosslinked; pendant hydrogen bonding groups are present on the pendant and/or side chains of the polymer chain.

The first network structure is obtained by covalently crosslinking a compound containing the bondable exchangeable covalent bond group and a compound having a side hydrogen bond group. As an example, it is not limited to the following, for example, a dithiol containing an exchangeable covalent bond group (in the following structural formula, V _m , V _m conforming to the structure of one of the formula (1) or (2)) The monomer and the pendant group have a side hydrogen bond group (hereinafter referred to as R _H in the structural formula, and R _H at least conforms to the structure of one of the formula (3) or (4), and is selected to conform to the formula (3) and a structure of 4); preferably a diolefin monomer having a hydrogen bond formed by R _H not more than four teeth) and a side group active hydrogen group (hereinafter referred to as R _g in the structural formula, R _{g is} selected from a hydroxyl group, an amino group (see V _m The choice of the group can be used for the transesterification reaction and the amine exchange reaction)) of the terminal multiolefin crosslinker which can be polymerized/crosslinked to form the first network structure of the present invention. Covalent cross-linking in the network is achieved above the covalent gel point by controlling the formulation ratio of the monomer and crosslinker.

In another example, a diazide monomer having an exchangeable covalent bond group V _m and a diacetylenic monomer having a side hydrogen bond group R _H and a terminal polyacetylene having a pendant base active hydrogen group R _g The hydrocarbon crosslinking agent can be polymerized/crosslinked to form the first network structure in the present invention. Covalent cross-linking in the network is achieved above the covalent gel point by controlling the formulation ratio of the monomer and crosslinker.

As another example, it can also be achieved by a radical polymerization reaction. The first network structure in the present invention can be obtained by radical polymerization of an olefin with an olefin having a hydroxyl group at the terminal, an olefin having a side hydrogen bond group at the terminal, and a diolefin having an ester group. Covalent cross-linking in the network is achieved above the covalent gel point by controlling the formulation ratio of monoolefins and diolefins.

In addition, covalent crosslinking means containing a bondable exchangeable covalent bond group can also be produced while crosslinking. By way of example and not limitation, for example, covalent cross-linking of a dicarboxylic acid compound and a diepoxy compound having a _RH group and a polyvalent epoxy compound having a pendant group form the first network structure in the present invention. Covalent cross-linking in the network is achieved above the covalent gel point by controlling the formulation ratio of the monomer and crosslinker.

As another example, covalent cross-linking of a diacid chloride compound and a diamine compound having a R _H group and a polyamine compound having a pendant group form the first network structure in the present invention. Covalent cross-linking in the network is achieved above the covalent gel point by controlling the formulation ratio of the monomer and crosslinker. In addition, the ratio of the acid chloride group and the amino group in the reaction material should be controlled according to the situation, so that a part of the amino group is reserved on the crosslinked network to participate in the amide exchange reaction.

Wherein, the R _H group carried by the above pendant group may be previously formed before the polymerization/crosslinking.

The implementation of other network structures in the present invention is similar to this, and those skilled in the art can select appropriate preparation means according to the understanding of the present invention to achieve the desired purpose.

The dynamic polymer of the present invention having a hybrid crosslinked network can be based on a multi-network structure of two or more networks, except that the network structure can have one and only one polymer network. In addition to conventional blend dispersion, an interpenetrating network formed by intertwining two or more polymer networks with each other is more preferred. The interpenetrating network polymer structure is superior to the single-network polymer of its components due to the synergy between the network components, resulting in higher toughness and other mechanical properties than the single network, especially based on the design idea of the present invention. In the case of hydrogen bonding crosslinks.

In the present invention, the cross-linking of the polymer components in the composition interpenetrating network can be divided into two types, semi-interpenetrating and fully interpenetrating. In the semi-interpenetration, only one component is covalently crosslinked, and the other component is interspersed in the covalently crosslinked component in the form of a non-covalently crosslinked molecular chain. If the supramolecular cross-linking is neglected, the second network structure and the fourth network structure of the present invention belong to a semi-interpenetrating network, and the third network structure and the fifth network structure of the present invention belong to full interpenetration. The network, the sixth network structure of the present invention has both semi-interpenetration and full interpenetration.

Conventional interpenetrating network polymer preparation methods generally include one-step interpenetration and two-step interpenetration. One-step method is to add all the ingredients at one time, and then carry out polymerization/cross-linking to prepare a target network. The two-step process first prepares the first network polymer, which is then immersed in the monomer/prepolymer solution forming the second network, and then initiates polymerization/crosslinking to obtain the target hybrid network. The preparation of the dynamic polymer having a hybrid crosslinked network in the present invention can also be carried out by one-step interpenetration and two-step interpenetration, and in a specific case, three steps or more must also be employed.

Embodiments of the partial preparation method of the interpenetrating network polymer of the present invention are exemplified below.

For example, in the second network structure of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks. Covalent cross-linking in the first network reaches above a gel point of covalent cross-linking, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond; its pendant/side chain The side hydrogen bond group is not contained; the second network does not contain covalent crosslinks, but side hydrogen groups are present on the side groups and/or side chains of the polymer chain. First, a linear polymer containing no covalent crosslinks but having pendant groups and/or side chains of a polymer chain containing hydrogen bonding groups was prepared as the second network. Then, in the preparation of the first network, the second network and the monomer of the first network, the crosslinking agent, and the like are uniformly mixed, and then covalently crosslinked by the covalent crosslinking means to obtain the first network and the first network. 2 The semi-interpenetrating network polymer of the network, that is, the first network is dispersed in the second network. Alternatively, the first network may be formed first, and then the second network may be recombined with the first network by swelling (by means of a solvent).

For example, in a fifth network structure of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks. Covalent cross-linking in the first network and the second network reaches above a covalent gel point; wherein the covalent cross-linking contains at least one of the bound exchangeable covalent bond crosslinks; the side of the polymer chain Side hydrogen bonding groups are present on the base and/or side chain. First, a prepolymer of the first network or the first network is prepared by the above-described covalent crosslinking means. Then, in the preparation of the second network, the prepolymer of the first network or the first network, the monomer of the second network, the crosslinking agent, and the like are first uniformly mixed, and then covalently crosslinked by the covalent crosslinking means. Thereby obtaining a fully interpenetrating network polymer of the first network and the second network. In this preparation method, it is preferred that the covalent gel point of the first network is a slight cross-linkage above the gel point, which is advantageous for the interpenetrating effect of the second network.

In an embodiment of the present invention, the binding in the dynamic polymer may exchange a covalent bond group and a supramolecular hydrogen bond group, which may be formed during the preparation of the dynamic polymer, or may constitute a dynamic The raw material component of the polymer itself is originally contained.

Suitable polymerization methods described in the embodiments of the present invention may be carried out by any suitable polymerization reaction generally used in the art including, but not limited to, condensation polymerization, addition polymerization, ring opening polymerization. ;among them, Addition polymerization reactions include, but are not limited to, radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. In a specific implementation, the compound starting material can be carried out by any of the above-described polymerization methods by any suitable polymerization process generally used in the art to obtain a dynamic polymer.

For the cross-linking mechanism of the polymer, it may be cross-linking and condensation crosslinking. Among them, the addition of a cross-linking refers to a cross-linking polymerization reaction carried out by an addition form, usually a cross-linking product is formed by an addition reaction of a polyfunctional group-containing molecular chain through an intermolecular functional group, and no by-product is produced. Condensation crosslinking refers to a crosslinking reaction carried out by a condensation form, usually by a molecular chain containing a polyfunctional group, which is formed by a condensation reaction of an intermolecular functional group to form a crosslinked product, and a by-product is produced.

In a particular implementation, cross-linking can employ any suitable physical and chemical crosslinking process. In the present invention, a compound containing the bound exchangeable covalent bond is usually used as a crosslinking agent for crosslinking, and a compound containing the binding exchangeable covalent bond may be directly crosslinked and/or Crosslinking is carried out in the presence of a crosslinking agent. Physical crosslinking processes include, but are not limited to, thermally induced crosslinking, photoinitiated crosslinking, radiation induced crosslinking, plasma initiated crosslinking, and microwave initiated crosslinking; chemical crosslinking processes include peroxide crosslinking, nucleophile replacement Linkage, isocyanate reaction cross-linking, epoxy reaction cross-linking, acrylate reaction cross-linking. The crosslinking process can be carried out in the form of a bulk, a solution, an emulsion or the like. When the bulk form is adopted, it is convenient to directly obtain the solid end product; when the solution form is used, it is convenient to directly obtain the gel; when the emulsion method is adopted, it is convenient to obtain the dispersed but self-adhesive particles. It is noted that any cross-linking must ensure that complete or incomplete dissociation of the bound exchangeable covalent bond can result in disintegration of the covalently crosslinked network.

In an embodiment of the invention, a certain proportion of the reaction mass may be mixed to prepare a dynamic polymer by any suitable mixing of materials known in the art, which may be a batch, semi-continuous or continuous process mixture; The dynamic polymer can also be shaped 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 embodiment of the present invention, the solution is stirred and mixed by melt stirring, and the mixing is mainly carried out in the following two ways: (1) the reaction material is directly stirred or mixed in the reactor or heated and melted, and then the mixture is stirred and mixed. The reaction material is a liquid or a solid having a relatively low melting point, or the reaction material is difficult to find a common solvent; (2) the reaction material is dissolved in a respective solvent or a common solvent is stirred and mixed in the reactor. The manner is generally used in the case where the reaction mass is a solid having a higher melting point or a fixed melting point. Usually, the mixing 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 1 to 12 hours, preferably 10 to 120 minutes. The product obtained after the mixing and stirring is poured into a suitable mold, and placed at 0-150 ° C, preferably 25-80 ° C, for 0-48 h to obtain a polymer sample, in which case the solvent can be removed as needed.

The solvent used in the above preparation method must be capable of dissolving the reaction materials simultaneously or separately, and the solvent in which the two types of compounds are dissolved must be mutually soluble, and the reaction materials are not precipitated in the mixed solvent, and the solvent used includes but is not limited to any of the following Or a mixed solvent of any solvent: deionized water, methanol, ethanol, acetonitrile, acetone, methyl ethyl ketone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, chloroform, dichloro Methane, 1,2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, n-butyl acetate, trichloroethylene, Trimethylbenzene, dioxane, Tris buffer, citrate buffer, acetic acid buffer solution, phosphate buffer solution, boric acid buffer solution, etc.; preferably deionized water, methanol, toluene, chloroform, dichloro Methane, 1,2-dichloroethane, dimethylformamide, phosphate buffer solution.

In the embodiment of the present invention, a specific preparation method for preparing a dynamic polymer material by melt extrusion mixing is generally: adding a certain amount of the reaction material to an extruder for extrusion blending reaction, and the extrusion temperature is 0-280. °C, preferably 25-150 ° C, more preferably 50-100 ° 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 25-150 ° C, more preferably 50-100 ° C; the molding temperature is 0-280 ° C, preferably 25-150 ° C, more preferably 50-100 ° C, the molding time is 0.5-60 min, It is preferably 1-10 min. The spline is placed in a suitable mold and placed at a temperature of 25-150 ° C, preferably 50-80 ° C, for 0-24 h to obtain a final polymer sample.

In an embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network may exist in the form of not only ordinary solid materials but also gels and foams.

In an embodiment of the invention, a dynamic polymer gel having a hybrid crosslinked network can be prepared by introducing a solvent, a plasticizer, or the like into a dynamic polymer having a hybrid crosslinked network. The solvent, plasticizer, and the like may include, but are not limited to, an organic solvent, an ionic liquid, an oligomer, a plasticizer, and water.

The invention provides a dynamic polymer gel with a hybrid crosslinked network, which comprises an organic solvent gel, an ionic liquid gel, an oligomer swollen gel, a plasticizer swollen gel, and a hydrogel. Among them, an ionic liquid gel and a plasticizer swollen gel are preferred, and a plasticizer swollen gel is more preferred.

The method for preparing a dynamic polymer ionic liquid gel of the present invention preferably comprises the steps of: adding a raw material of a dynamic polymer for preparing a hybrid crosslinked network to an ionic liquid to prepare a hybrid crosslinked network; The dynamic polymer has a mass fraction of 0.5 to 50%, is covalently crosslinked by the appropriate means, and after the reaction is finished, it is naturally cooled to prepare a dynamic polymer gel. The ionic liquid is generally composed of an organic cation and an inorganic anion, and the cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphonium ion, a 1,3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion, or the like. The anion is usually a halogen ion, a tetrafluoroborate ion, a hexafluorophosphate ion, 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. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion and a tetrafluoroborate ion.

The method for preparing a dynamic polymer plasticizer swollen gel of the present invention preferably comprises the steps of: adding a raw material of a dynamic polymer having a hybrid crosslinked network to a plasticizer, so that the prepared hybridized The dynamic polymer of the network has a mass fraction of 0.5 to 50%, and is covalently crosslinked by the appropriate means. After the reaction is completed, it is naturally cooled to form a gel which is swollen by a dynamic polymer plasticizer. The plasticizer is selected from any one or more of the following: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, ortho-benzene Diheptyl dicarboxylate, diisononyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate glycolate, dicyclohexyl phthalate Ester, bis(tridecyl) phthalate, di(2-ethyl)hexyl terephthalate; phosphates such as tricresyl phosphate, diphenyl-2-ethylhexyl phosphate; Fatty acid esters such as di(2-ethyl)hexyl adipate, di(2-ethyl)hexyl sebacate; epoxy compounds such as epoxy glycerides, epoxidized fatty acid monoesters, Epoxy tetrahydrophthalate, epoxidized soybean oil, (2-ethylhexyl) epoxy stearate, 2-ethylhexyl epoxide, 4,5-epoxytetrahydrogen Di(2-ethylhexyl) phthalate, methyl acetyl ricinoleate, glycol esters, such as C _5-9 acid glycol, C _5-9 acid triethylene glycol Ester; chlorine-containing, such as green paraffin, chlorinated fatty acid ester; polyester, such as B Acid 1,2-propanediol polyester, sebacic acid 1,2-propanediol polyester; petroleum sulfonic acid phenyl ester, trimellitate citrate, pentaerythritol, dipentaerythritol and the like. Among them, epoxidized soybean oil is an environmentally-friendly plastic plasticizer with excellent performance, which is prepared by epoxidation of refined soybean oil and peroxide. It is resistant to volatilization, difficult to migrate and difficult to disperse in PVC products. This is very beneficial for maintaining the light, thermal stability and longevity of the product. Epoxidized soybean oil is extremely toxic and has been approved for use in food and pharmaceutical packaging materials in many countries. It is the only epoxy plasticizer approved by the US Food and Drug Administration for use in food packaging materials. In the preparation of a dynamic polymeric plasticizer swollen gel of the present invention, the plasticizer is preferably epoxidized soybean oil.

In embodiments of the invention, the dynamic polymer of the hybrid crosslinked network may also be swelled into a gel using oligomers including, but not limited to, polyethylene glycol oligomers, polyvinyl alcohol oligomers , polyvinyl acetate oligomer, polybutyl n-butyl acrylate oligomer, liquid paraffin, and the like.

In an embodiment of the invention, a dynamic polymer having a hybrid crosslinked network can be prepared as a foamed material. Among them, the foam includes a flexible foam, or a semi-flexible, semi-rigid, microporous or rigid foam. The foaming method can be classified into two categories, physical foaming method and chemical foaming method, depending on the foaming agent used. The foam can be prepared in the presence of water or anhydrous, and can be mechanically or non-mechanically foamed. Further, the foam may use an auxiliary non-reactive blowing agent known in the art.

In the embodiment of the present invention, the structure of the dynamic polymer foam material involves three types of an open-cell structure, a closed-cell structure, and a half-open half-close structure. 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 gas or 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 to 3 mm. The cells contained in the cells are connected to each other and have a semi-open structure.

A method for preparing a dynamic polymer foam of the present invention comprises the steps of: in preparing a single network dynamic polymer foam, the reaction material A: 1 part to 100 parts of all small molecules participating in the reaction, and 0.05 part of a chain extender ～1.0 parts, 0.05 parts to 1.0 parts of cross-linking agent, and stirred evenly under the stirring speed of 50-200r/min; reaction material B: foaming agent 0.5 parts to 6 parts, foam stabilizer 0.05 parts to 0.2 parts, catalyst 0.01 ～1.0 parts, stir evenly under the stirring speed of 50～200r/min; then mix the reaction material A and the reaction material B according to the mass ratio of 1:1～3:1, stir rapidly by professional equipment, and heat as needed. The temperature is raised to obtain a foamed single network dynamic polymer.

In the dynamic polymer foam preparation method of the present invention, when a plurality of networks are contained in the foam, a plurality of networks may be simultaneously generated or separately formed.

The dynamic polymeric foam material provided by the present invention also relates to converting the dynamic polymeric foam material into any desired shape by welding, gluing, cutting, gouging, perforating, stamping, laminating, and thermoforming. For example, tubes, rods, sheaths, containers, balls, sheets, rolls, and tapes; dynamic polymeric foams with sheets, films, foams, fabrics, reinforcements by lamination, bonding, fusing, and other joining techniques And a combination of other materials known to those skilled in the art to form a complex sandwich structure; the use of the dynamic polymer foam material in a gasket or seal; the dynamic polymer foam material in a packaging material or in a container use. With respect to the dynamic polymers of the present invention, the foamable dynamic polymers are of a type that allows them to be deformed by extrusion, injection molding, compression molding, or other forming techniques known to those skilled in the art.

The foaming material provided by the invention is different from the ordinary foam material. Once the three-dimensional structure prepared by the ordinary foam material is shaped, the structure can no longer be changed, the repair is difficult, and it cannot be recycled after the damage. Since the foamed material provided by the present invention is a covalently crosslinked polymer network, it can be repaired after rupture under certain conditions, or can be reused by reshaping or recycling, because of the network structure. There are both hydrogen bonding and binding exchangeable covalent bonds. The foaming material provided by the invention solves the problem of remodeling, controllable repair and recycling of common foam materials.

In the preparation process, the dynamic polymer material of the invention may also add certain additives and fillers to form a dynamic polymer material, which can improve the material preparation process, improve product quality and yield, reduce product cost or impart The product has some unique application properties, but these additives are not required.

The additive which can be added is selected from any one or any of the following auxiliary agents: a synthesis auxiliary agent, including a catalyst, an initiator, a stabilization aid, including an antioxidant, a light stabilizer, a heat stabilizer; Additives for mechanical properties, including toughening agents, coupling agents; additives to improve processing properties, including lubricants, mold release agents; softening and lightening additives, including plasticizers; Agents, including antistatic agents, emulsifiers, dispersants; additives for changing shades, including colorants, fluorescent whitening agents, matting agents; flame retardant and smoke suppressing additives, including flame retardants; other additives, including A bactericidal fungicide, a dehydrating agent, a nucleating agent, a rheological agent, a thickener, a thixotropic agent, a leveling agent; an auxiliary agent for preparing a foaming material, including a chain extender, a foam stabilizer, and a foaming agent.

The catalyst in the additive additive which can be added can increase the reaction rate by changing the reaction pathway and reducing the activation energy of the reaction, for example, cycloaddition polymerization (CuAAC reaction) of an azide compound and an alkyne. 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. The amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.

In the embodiment of the present invention, the catalyst for reacting a carboxylic acid and an epoxy compound may, for example, be zinc acetate, zinc acetylacetonate, 2-methylimidazole, chromium 3,5-diisopropylsalicylate, or the like. Chromium 5-di-tert-butylsalicylate; substituted chromium furancarboxylate, such as chromium 5-tert-butylfurancarboxylate, chromium 5-phenylacylfurancarboxylate, chromium 5-isopropylfurancarboxylate, 3,5-di Chromium isopropyl furancarboxylate; chromium fatty acid, such as chromium 2-ethylhexanoate, chromium naphthenate. Among them, 2-methylimidazole, zinc acetate, zinc acetylacetonate, chromium 3,5-diisopropylsalicylate, and chromium 5-isopropylfurancarboxylate are preferable. The amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.

In the embodiment of the present invention, examples of the catalyst for reacting a hydroxyl group, an amino group or a mercapto group with an isocyanate include the following amine catalysts and organometallic compound catalysts. The amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.

As the amine catalyst, including but not limited to any one or any of the following catalysts: triethylamine, triethylenediamine, bis(dimethylaminoethyl)ether, 2-(2-dimethylamino-ethoxyl) Ethyl alcohol, trimethyl hydroxyethyl propylene diamine, 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'- Tetramethylalkylene diamine, N,N,N',N',N'-pentamethyldiethylenetriamine, N,N-dimethylethanolamine, N-ethylmorpholine, 2, 4,6-(dimethylaminomethyl)phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine and the like.

As the organometallic catalyst, including but not limited to any one or any of the following catalysts: organotin compounds 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.

In the embodiments of the present invention, other reactions between reactive groups also require an initiator, such as a thiol-double bond click reaction, an acrylate radical reaction, and a double bond-double bond coupling process, requiring a free radical initiator. It can cause activation of monomer molecules during the polymerization reaction to generate radicals, increase the reaction rate, and promote the reaction. The initiator includes, but is not limited to, any one or more of the following: a photoinitiator such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2- Methyl-1-phenylacetone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy- 4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and α- Ketoglutaric acid. Organic peroxides such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate 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 2,2-dimethoxy-2-phenylacetophenone, azodi Isobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate. The double-bond-double bond coupling reaction can also be carried out by means of radiation polymerization, using high-energy ionizing radiation (such as α-ray, β-ray, γ-ray, x-ray, electron beam) to radiate monomer to generate ions or free radicals to form an active center. And the aggregation occurs. In the embodiments of the present invention, a suitable initiator and polymerization mode can be selected depending on the circumstances. The amount of the initiator to be used is not particularly limited and is usually from 0.01 to 2% by weight.

The antioxidant in the additive which can be added, which can delay the oxidation process of the polymer material, ensure that the material can be processed smoothly and prolong its service life, including but not limited to any one or any of the following Agent: hindered phenols, such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl)butane, four [β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol); sulfur 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'-di Phenyl p-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine; sulfur-containing, such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; Phosphites, such as triphenyl phosphite, phosphorous Trimethylphenyl phenylate, tris[2.4-di-tert-butyl Phenyl]phosphite, etc., wherein 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), tetrakis[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 additive which can be added can prevent photoaging of the polymer material 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) -Hydroxy-4-n-butoxyphenyl)-1,3,5-s-triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; pioneer UV absorber, such as water P-tert-butylphenyl salicylate, 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-tertiary Butyl-4-hydroxybenzoic acid (2,4-di-tert-butylbenzene) , Alkylphosphoric acid amide, N, N'- di-n-butyl dithiocarbamate, zinc, N, N'- di-n Dingzheng Ji nickel dithiocarbamate. Among them, the light stabilizer is preferably carbon black, bis(2,2,6,6-tetramethylpiperidine) sebacate (light stabilizer 770), and the amount of the light stabilizer used is not particularly limited, and is generally 0.01- 0.5 wt%.

The heat stabilizer in the additive which can be added can make the polymer material not undergo chemical changes 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 the following Any or any of several heat stabilizers: lead salts, such as tribasic lead sulfate, lead dibasic phosphite, lead dibasic stearate, lead dibasic lead, tribasic Malay Lead acid, lead-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 , barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di(n-butyl)butylate, Bi-maleic acid monooctyl ester di-n-octyltin, di-mercaptoacetic acid isooctyl ester di-n-octyltin, jingxi C-102, di-mercaptoacetic acid isooctyl dimethyl tin, dithiol dimethyl tin and its compound锑Stabilizers, such as thiol sulfonium salts, thioglycol thiol thiols, hydrazino carboxylates, carboxylic acid esters 锑Epoxide compounds such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites such as triaryl phosphite, trialkyl phosphite, triaryl phosphite, alkane mixed esters, Polymeric phosphites; polyols such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; composite heat stabilizers such as coprecipitated metal soaps, liquid metal soap composite stabilizers, organotins Composite stabilizers, etc. Among them, the heat stabilizer is preferably barium stearate, calcium stearate, di-n-butyltin dilaurate or di(n-butyltin) maleate, and the amount of the heat stabilizer to be used is not particularly limited, and is usually 0.1 to 0.5% by weight.

The toughening agent in the additive can reduce the brittleness of the polymer material, 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: methacrylic acid Ester-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, ethylene propylene diene rubber, cis butyl rubber, styrene butadiene rubber, styrene-butadiene-styrene block copolymer, and the like. Among them, the toughening agent is preferably ethylene propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butyl The amount of the toughening agent to be used is not particularly limited, and is usually from 5 to 10% by weight based on the styrene-styrene copolymer resin (MBS) and the chlorinated polyethylene resin (CPE).

The coupling agent in the additive can improve the interfacial properties of the polymer material and the inorganic filler or 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. , in turn, to obtain 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 A crosslinking agent, a sulfonyl azide coupling agent, an aluminate coupling agent, and the like. Among them, γ-aminopropyltriethoxysilane (silane coupling agent KH550) and γ-(2,3-epoxypropoxy)propyltrimethoxysilane (silane coupling agent KH560) are preferably used. The amount of the crosslinking agent is not particularly limited and is usually from 0.5 to 2% by weight.

The lubricant in the additive that can be added can improve the lubricity of the material, reduce friction, and reduce interfacial adhesion. It includes, but is not limited to, any one or any of the following lubricants: saturated hydrocarbons and halogenated hydrocarbons such as paraffin wax, microcrystalline paraffin, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as hard Fatty 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, stearic acid Calcium, barium stearate, magnesium stearate, zinc stearate, and the like. Among them, the lubricant is preferably solid paraffin, liquid paraffin, stearic acid or low molecular weight polyethylene, and the amount of the lubricant to be used is not particularly limited and is usually from 0.5 to 1% by weight.

a mold release agent in the additive which can easily release the polymer sample, and the surface is smooth and clean, including but not limited to any one or any of the following mold release agents: paraffin hydrocarbon, soap , Dimethicone, Ethyl Silicone, Methyl Phenyl Silicone Oil, Castor Oil, Waste Engine Oil, Mineral Oil, Molybdenum Disulfide, Polyethylene Glycol, Vinyl Chloride Resin, Polystyrene, Silicone Rubber, Polyvinyl Alcohol, etc. Among them, the release agent is preferably dimethicone or polyethylene glycol, and the amount of the lubricant to be used is not particularly limited and is usually from 0.5 to 2% by weight.

An optional plasticizer in the additive that can increase the plasticity of the polymer sample, resulting in a decrease in hardness, modulus, softening temperature, and embrittlement temperature of the polymer, elongation, flexibility, and flexibility. Improvement, including but not limited to any one or more of the following: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, ortho-benzene Diheptyl dicarboxylate, diisononyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate glycolate, dicyclohexyl phthalate Ester, bis(tridecyl) phthalate, di(2-ethyl)hexyl terephthalate; phosphates such as tricresyl phosphate, diphenyl-2-ethylhexyl phosphate; Fatty acid esters such as di(2-ethyl)hexyl adipate, di(2-ethyl)hexyl sebacate; epoxy compounds such as epoxy glycerides, epoxidized fatty acid monoesters, Epoxy tetrahydrophthalate, epoxidized soybean oil, epoxy linseed oil, (2-ethylhexyl) epoxy stearate, 2-ethylhexyl epoxide, 4, 5-epoxy four Phthalate, di (2-ethylhexyl) ester, epoxy acetyl methyl ricinoleate, diol lipids, such as C _5-9 glycol acrylate, triethylene glycol C _5-9 acid condensing Alcohol ester; chlorine-containing, such as green paraffin, chlorinated fatty acid ester; polyester, such as oxalic acid 1,2-propanediol polyester, azelaic acid 1,2-propanediol polyester; petroleum sulfonic acid benzene Ester, trimellitate, citrate, pentaerythritol and dipentaerythritol ester; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), orthophthalic acid Diisooctyl formate (DIOP), diisodecyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP), epoxidized soybean oil and epoxy linseed oil. The amount of the plasticizer to be used is not particularly limited and is usually from 5 to 50% by weight.

The antistatic agent in the additive which can be added can guide or eliminate the harmful charges accumulated in the polymer material, so that it does not cause inconvenience or harm to production and life, including but not limited to any one of the following or Several antistatic agents: anionic antistatic agents, such as alkyl sulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate diethanolamine salts, alkylphenol polyoxyethylene ether sulfonic acid triethanolamine , p-Mercapto-diphenyl ether sulfonate, alkyl polyoxyethylene ether sulfonate triethanolamine, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ether alcohol ester, alkyl double [two (2 -Hydroxyethylamine)]phosphate, phosphate derivative, fatty amine sulfonate, sodium butyrate sulfonate; cationic antistatic agent, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, Dodecyltrimethylamine bromide, N,N-cetyl-ethylmorpholine ethyl sulfate, stearamidopropyl (2-hydroxyethyl)dimethylammonium nitrate, alkyl hydroxyethyl Methylammonium perchlorate, 2-alkyl-3,3-dihydroxyethyl imidazoline perchlorate, 2-heptadecyl-3-hydroxyethyl-4-carboxymethylimidazoline, N, N-double (α -Hydroxyethyl)-N-3 (dodecyloxy-2-hydroxypropyl)methylammonium methyl sulfate; 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, alkane Bis(polyoxyethylene) ammonium beta salt, 2-alkyl-3hydroxyethyl-3-acetate imidazoline quaternary amine base, N-alkyl amino acid salt; nonionic antistatic agent , such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, alkyl phenol ethylene oxide adduct, triethoxy oxyethylene ether phosphate, glycerol mono-fatty acid ester, water loss Yamanashi Polyethylene oxide adduct of alcohol monolaurate; polymer type antistatic agent, such as ethylene oxide propylene oxide adduct of ethylenediamine, polyethylene glycol-terephthalate- A sodium 3,5-dibenzoate sulfonate copolymer, a polyallylamide N-quaternary ammonium salt substitute, a poly-4-vinyl-1-acetoxypyridine phosphate-p-butylphenyl ester salt, and the like. Among them, lauryl trimethyl ammonium chloride and octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (antistatic) are preferred. The electric agent SN), the alkyl phosphate diethanolamine salt (antistatic agent P), and the amount of the initiator to be used are not particularly limited, and are usually from 0.3 to 3% by weight.

The emulsifier in the additive which can be added 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, including but not only 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 sulfonates, petroleum sulphur Acid salt, 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, alkane Pyridinium salt; zwitterionic type, such as carboxylate type, sulfonate type, sulfate type, phosphate type; nonionic type, such as fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxygen Vinyl ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol amine fatty acid amide, and the like. Among them, sodium dodecylbenzenesulfonate, sorbitan fatty acid ester, and triethanolamine stearate (emulsifier FM) are preferred, and the amount of the emulsifier used is not particularly limited, and is usually from 1 to 5% by weight.

The dispersing agent in the additive which can be added enables the solid floc cluster in the polymer mixture to be dispersed into fine particles and suspended in the liquid, uniformly dispersing solid and liquid particles which are difficult to be dissolved in the liquid, and can also prevent Settling and agglomeration of the particles 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, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic type, such as silicate, condensed phosphate; polymer type, such as starch, gelatin, water-soluble glue , lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonate, polyvinyl alcohol, β-naphthalenesulfonic acid formaldehyde condensate, alkyl phenol formaldehyde condensate ethylene oxide Condensate, polycarboxylate, and the like. The dispersing agent is preferably sodium dodecylbenzenesulfonate, naphthalene methylenesulfonate (dispersant N), or fatty alcohol polyoxyethylene ether. The amount of the dispersing agent used is not particularly limited, and is generally 0.3-0.8 wt. %.

The colorant in the additive that can be added can cause the polymer product to exhibit a desired color and increase the surface color, including but not limited to any one or any of the following colorants: inorganic pigments such as titanium white, 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, Yong Solid 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 and so on. The coloring agent is selected depending on the color requirement of the sample, and is not particularly limited. The amount of the coloring agent to be used is not particularly limited and is usually from 0.3 to 1.0% by weight.

The optical brightener in the additive which can be added enables the dyed material to obtain a fluorite-like sparkling effect, including but not limited to any one or any of the following fluorescent whitening agents: stilbene Type, coumarin type, pyrazoline type, benzoxyl type, phthalimide type, and the like. Among them, the fluorescent whitening agent is preferably sodium stilbene biphenyl disulfonate (fluorescent whitening agent CBS), 4,4-bis(5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening) Agent KSN), 2,2-(4,4'-distyryl) bisbenzoxazole (fluorescent brightener OB-1), the amount of fluorescent whitening agent used is not particularly limited, and is generally 0.002-0.03 Wt%.

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

The flame retardant in the additive which can be added 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, cresyl phosphate, phosphoric acid Triphenyl ester, tricresyl phosphate, toluene diphenyl phosphate; halogen-containing phosphates such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl) phosphate; organic Halides, such as high chlorine content chlorinated paraffin, 1,1,2,2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentanane; inorganic flame retardants, such as antimony trioxide, hydrogen Alumina, magnesium hydroxide, zinc borate; reactive flame retardants, such as chloro-bromic anhydride, bis(2,3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromo-o-phenyl Formic anhydride and the like. The flame retardant is preferably decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate or antimony trioxide. The amount of the flame retardant used is not particularly limited. It is 1-20% by weight.

The bactericidal antifungal agent in the additive can inhibit the growth of mold, maintain the neat appearance of the product, prolong the service life, or protect the user and improve the health of the user, such as reducing athlete's foot. These include, but are not limited to, any one or more of the following: isothiazolinone derivatives such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazole Benz-3-one, N-n-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone; 2,4,4-trichloro-2-hydroxy-diphenyl ether ; 2-(4-thiazolyl)benzimidazole; copper 8-hydroxyquinolate or bis(8-hydroxyquinolinyl) copper; organotin compounds such as tributyltin fumarate, tributyltin acetate, bis(tributyltin) Sulfide, bis(tributyltin)tin oxide; N,N-dimethyl-N'-phenyl(fluorodichloromethylthio)sulfonamide; inorganic compound or composite such as nanosilver, nano titanium dioxide, nano Silica, nano zinc oxide, ultrafine copper powder, inorganic antibacterial agent YY-Z50, XT inorganic antibacterial agent, and composite antibacterial agent KHFS-ZN. The amount of the bactericidal fungicide to be used is not particularly limited and is usually from 0.5 to 5% by weight.

The nucleating agent in the additive which can be added can shorten the molding cycle of the material, improve the transparency of the product, and improve the crystallization rate of the polymer, accelerate the crystallization rate, increase the crystal density, and promote the grain size miniaturization. The purpose of physical and mechanical properties such as gloss, 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 monomer, and the like. Among them, the nucleating agent is preferably silica, dibenzylidene sorbitol (DBS) or ethylene propylene diene rubber. The amount of the nucleating agent to be used is not particularly limited, but is usually 0.1 to 1% by weight.

The dehydrating agent in the additive which can be added can remove moisture in the system, including but not limited to any one or more of the following: an oxazolidine compound (such as 3-ethyl-2-methyl-2) -(3-methylbutyl)-1,3-oxazolidine), p-toluenesulfonyl isocyanate, triethyl orthoformate, vinyl silane, calcium oxide, and the like. The amount of the dehydrating agent to be used is not particularly limited and is usually from 0.1 to 2% by weight.

The rheological agent in the additive which can be added can ensure good paintability and proper film thickness of the polymer in the coating process, prevent sedimentation of solid particles during storage, and can improve redispersibility thereof. These include, but are not limited to, any one or any of the following rheological agents: inorganic, 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 alkoxide, titanium chelate, aluminum chelate; organic, such as organic bentonite, hydrogenated castor oil, hydrogenated castor oil / amide Wax, cellulose derivative, isocyanate derivative, hydroxy compound, acrylic emulsion, acrylic copolymer, polyvinyl alcohol, polyethylene wax, cellulose ester, and the like. Among them, organic bentonite, polyethylene wax, hydrophobically modified alkaline swellable emulsion (HASE), and alkali swellable emulsion (ASE) are preferable, and the amount of the rheology agent to be used is not particularly limited, and is usually 0.1 to 1% by weight.

The thickener in the additive which can be added 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, fatty alcohol polyoxyethylene ether sulfates, alkyl dimethylamine oxides, fatty acid monoethanolamides, fatty acids Diethanolamide, fatty acid isopropylamide, sorbitan tricarboxylate, glycerol trioleate, cocoamidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline, titanium Acid ester coupling agent; high molecular substance, such as bentonite, artificial hectorite, fine powder silica, colloidal aluminum, plant polysaccharides, microbial polysaccharides, animal protein, cellulose, starch, alginic acid , polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, crotonic acid copolymer, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyether, polyvinyl methyl ether urethane polymer, and the like. Among them, the thickener is preferably hydroxyethylcellulose, coconut oil diethanolamide or acrylic acid-methacrylic acid copolymer, and the amount of the thickener to be used is not particularly limited, and is usually 0.1 to 1.5% by weight.

The thixotropic agent in the additive can be added to the dynamic polymer system to form a three-dimensional network structure with the polymer molecules through hydrogen bonding, so that the dynamic polymer viscosity is increased several times to many times, and even the fluidity is lost. These include, but are not limited to, any one or more of the following: fumed silica, hydrogenated castor oil, bentonite, silicic anhydride, silicic acid derivatives, urea derivatives, and the like. The amount of the thixotropic agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.

The leveling agent in the additive can ensure the smoothness and uniformity of the polymer coating film and improve the surface quality of the coating film Amount, improve decorative, including but not limited to any one or any of the following leveling agents: polydimethylsiloxane, polymethylphenylsiloxane, cellulose acetate butyrate, polyacrylate Class, silicone resin, etc. Among them, the leveling agent is preferably polydimethylsiloxane or polyacrylate, and the amount of the thickener to be used is not particularly limited and is usually from 0.5 to 1.5% by weight.

In the preparation process of the foam material, it is also necessary to add a chain extender, a foam stabilizer, a foaming agent and the like according to actual conditions.

Specific examples of the chain extender include ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1,4-butanediol, and 1,6-hexanediol. , hydroquinone dihydroxyethyl ether (HQEE), resorcinol bishydroxyethyl ether (HER), p-dihydroxyethyl bisphenol A, triethanolamine, triisopropanolamine, diaminotoluene, two Aminoxylene, tetramethylxylylenediamine, tetraethyldibenzylidenediamine, tetraisopropyldiphenylylenediamine, m-phenylenediamine, tris(dimethylaminomethyl) Phenol, diaminodiphenylmethane, 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 3,5-dimethylthiotoluenediamine (DMTDA), 3,5 -Diethyl toluenediamine (DETDA), 1,3,5-triethyl-2,6-diaminobenzene (TEMPDA). The amount of the chain extender to be used is not particularly limited and is usually from 0.1 to 25 % by weight.

In an embodiment of the invention, a foam stabilizer for making a foamed material is an organopolysiloxane surfactant. Such organosiloxane surfactants are generally block copolymers of polydimethylsiloxane and polyalkylene oxide. The amount of the foam stabilizer to be used is not particularly limited and is usually from 0.1 to 5 % by weight.

In the embodiment of the present invention, the foaming agent for preparing the foamed material may be a physical foaming agent or a chemical foaming agent. The utility model has high surface activity, can effectively reduce the surface tension of the liquid, and is arranged in the double electron layer on the surface of the liquid film to surround the air to form bubbles, and then the foam is composed of a single bubble.

The physical blowing agent includes, but is not limited to, any one or any of the following blowing agents: air, carbon dioxide, nitrogen, freon (such as HCFC-141b, HCFC-123, HCFC-22, HCFC-365mfc, HCFC- 245fa, etc., dichloromethane, trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, n-pentane, cyclopentane, isopentane, physical microspheres/particle foaming agent, and the like. The chemical foaming agent includes, but is not limited to, any one or any of the following blowing agents: water, calcium carbonate, magnesium carbonate, sodium hydrogencarbonate, sodium silicate, carbon black, azo compounds (such as azo Amide (ADC), azobisisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazoaminobenzene, hydrazine azodicarboxylate, sulfonyl hydrazide (eg 4, 4-disulfonyl hydrazine diphenyl ether (OBSH), benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 2,4-toluene disulfonyl hydrazide, 3,3-disulfonyl hydrazide diphenyl sulfone, (N- Methoxyformylamino)benzenesulfonyl hydrazide), nitroso compound (such as N,N-dinitrosopentamethylenetetramine (DPT), N,N-dimethyl-N,N-di Terephthalamide (NTA) and the like. The blowing agents may be used singly or in combination of two or more. The amount of the blowing agent used is a usual amount, that is, 0.1 to 10 php, preferably 0.1 to 5 php in the case of using water, and about 0.1 to 20 php in the case of using a halogenated hydrocarbon, an aliphatic alkane and an alicyclic alkane. Where php represents the number of parts of the blowing agent per hundred parts of polymer polyol.

The additive which can be added mainly plays the following roles in the polymer sample: 1 reducing the shrinkage rate of the molded article, improving the dimensional stability, surface smoothness, smoothness, and flatness or mattness of the product; Adjust the viscosity of the material; 3 to meet different performance requirements, such as improving the impact strength and compressive strength, hardness, stiffness and modulus of the material, improving wear resistance, improving heat distortion temperature, improving electrical conductivity and thermal conductivity, etc.; 4 improving pigment coloration Effect; 5 imparts light stability and chemical resistance; 6 plays a compatibilizing role, which can reduce costs and improve the competitiveness of products in the market.

The filler that can be added 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 that can be added 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, carbon nanotubes, molybdenum disulfide, slag, flue ash, wood flour and shell powder, silicon Algae, red mud, wollastonite, silica-alumina, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, white mud, Alkaline mud, boron mud, glass beads, resin beads, foamed microspheres, foamable particles, glass powder, cement, glass fiber, carbon fiber, quartz fiber, carbon fiber boron fiber, titanium diboride fiber, titanic acid Calcium fiber, carbon silicon fiber, ceramic fiber, whisker, etc.

The metal filler that can be added includes, but is not limited to, any one or more of the following: conductive metal filler, metal particles Granules, nanoparticles, metal and alloy powders, carbon steel, stainless steel, stainless steel fibers, liquid metals, organometallic compounds (especially organometallic compounds with photothermal, magnetocaloric, electrothermal properties).

The organic fillers that can be added include, but are not limited to, any one or more of the following: 1 natural organic fillers such as fur, natural rubber, cotton, cotton linters, hemp, jute, linen, asbestos, cellulose, acetate , shellac, chitin, chitosan, lignin, starch, protein, enzymes, hormones, lacquer, wood, wood flour, shell powder, glycogen, xylose, silk, etc.; 2 synthetic resin fillers, such as acrylonitrile -Acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, cellulose acetate, polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymerization , ethylene-vinyl acetate copolymer, high density polyethylene, high impact polystyrene, low density polyethylene, medium density polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile , polyarylsulfone, polybenzimidazole, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polysulfone, polyethersulfone, polyparaphenylene Ethylene glycol diester, phenolic resin, four Fluoroethylene-perfluoropropane copolymer, polyimide, polymethyl acrylate, polymethacrylonitrile, polymethyl methacrylate, polyoxymethylene, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone , polystyrene, polytetrafluoroethylene, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, polyvinyl alcohol Formaldehyde, polyvinylpyrrolidone, urea-formaldehyde resin, ultra-high molecular weight polyethylene, unsaturated polyester, polyetheretherketone, etc.; 3 synthetic rubber fillers, such as isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, chloroprene Rubber, butyl rubber, ethylene propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, polysulfide rubber, urethane rubber, chloroether rubber, thermoplastic elastomer, etc.; 4 synthetic fiber fillers, such as viscose fiber, copper ammonia fiber , diethyl ester fiber, triethyl ester fiber, polyamide fiber, polycarbonate fiber, polyvinyl alcohol fiber, polyester fiber, polyurethane fiber, polyacrylonitrile fiber, polyvinyl acetal fiber, polyvinyl chloride fiber, poly Olefins Dimension, fluorine-containing fibers, polytetrafluoroethylene fibers, aramid fibers, aramid fibers or aramid fibers.

The type of filler to be added is not limited, and is mainly determined according to the required material properties, and preferably calcium carbonate, barium sulfate, talc, carbon black, graphene, glass microbeads, glass fibers, carbon fibers, natural rubber, chitosan. , starch, protein, polyethylene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl rubber , ethylene propylene rubber, silicone rubber, thermoplastic elastomer, polyamide fiber, polycarbonate fiber, polyvinyl alcohol fiber, polyester fiber, polyacrylonitrile fiber. The amount of the filler to be used is not particularly limited and is usually from 1 to 30% by weight.

The dynamic polymer with hybrid cross-linking network provided by the invention has wide range of properties and can be applied to various fields, and has broad application prospects, especially in military aerospace equipment, functional coatings and coatings, biomedicine. In the fields of biomedical materials, energy, construction, and bionics, it will have an impressive application effect. For example, by suitable component selection and formulation design, a polymer plugging agent with good plasticity and recyclability can be prepared; for example, a self-repairing function can be introduced into the polymer material, so that the inside of the material can be repaired by itself, and Helps to obtain structural materials that last longer, more reliable and more economical. For example, in the use of microelectronic polymer devices and adhesives, the loss of performance due to micro-cracks caused by thermal and mechanical fatigue is a long-standing problem. Introducing self-repairing functions into these materials can greatly improve the reliability and use of microelectronic products. life. As self-repairing plugs such as plugs and seals, they are widely used in electronics, food, medicine, etc., for example, as plugs for chargers, data line interfaces, etc. for mobile phones, tablets, notebooks, cameras, etc. The opening generated during the plugging and unplugging process is repaired to achieve waterproofing. As a self-healing material, it also helps to obtain materials with biomimetic effects. It also has broad application prospects in the biomedical field, and can obtain more durable human joints. As a self-healing material, it also contributes to the development of materials for special applications, such as materials that can restore interface properties, electrical conductivity, and thermal conductivity under certain conditions. For example, a binder as a battery electrode can reduce electrode breakage and increase the life of the electrode material. In addition, when used as a sacrificial bond, the supramolecular hydrogen bond can further enhance the toughness of the polymer, and can be prepared into a film, fiber or plate with excellent properties, which can be widely used in military, aerospace, sports, energy, construction. And other fields. Using strong dynamic hydrogen bond cross-linking responsiveness to stress/strain, materials with strong energy absorption and damping properties can be prepared for body protection in sports and daily life and work, military and police body protection, explosion protection, airborne and airdrop Protection, car crash, electronic material impact protection, speed locks for roads and bridges. In addition, use Its dynamic reversibility allows the preparation of shape-memory self-healing polymer materials that can be used to make toys with magical effects.

The dynamic polymer material of the present invention is further described below in conjunction 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

1,3-diglycidyl ether glycerol and methyl isocyanate are mixed in a molar ratio of 1:1, and reacted in dichloromethane under the catalysis of dibutyltin dilaurate to obtain a urethane having a urethane group in the pendant group. Ethane.

Trans-1,4-cyclohexanedicarboxylic acid and the above-mentioned pendant group containing urethane group-containing dioxirane are mixed at a molar ratio of 1:1, and 5 mol% of Zn(OAc) _{2 is added} as a bond exchange catalyst to prepare A dynamic polymer is obtained which contains a side hydrogen bond group and a bound exchangeable ester bond.

The obtained product also has good plasticity, can be placed in different shapes of the mold according to actual needs, and a certain stress is slightly applied under a certain temperature condition, and the polymer product of different shapes can be formed according to the mold. It can be made into a gasket material for use.

Example 2

Bicyclo [2.2.2] octane-1,4-cyclohexanedicarboxylic acid and SOCl2 ₂ according to a molar ratio of 1: 2 were mixed and reacted in DMF to give bicyclo [2,2,2] octane - 1,4-cyclohexanedichloride.

Pentaerythritol and butyl isocyanate are mixed in a molar ratio of 1:1, and are reacted in dichloromethane under the catalysis of dibutyltin dilaurate to obtain a triol compound having a urethane group in a pendant group.

Bicyclo[2,2,2]octane-1,4-cyclohexanediyl chloride and a trihydric alcohol compound having a urethane group as a side group described above are mixed at a molar ratio of 1:1, and 6 mol% of 2-MI and 5 mol% Zn(acac) ₂ was reacted in dichloromethane to prepare a dynamic polymer containing a side hydrogen bond group and a bound exchangeable ester bond.

The polymer sample has a certain strength and compressibility and can be stretched within a certain range. The sample after the breaking is applied with stress at the section (in this process, the section can be slightly wetted), and the section can be re-bonded after being heated in a mold of 100 ° C for 6 hours, which has self-repairing properties and can also be used according to different shapes of the mold. Reshape the material.

Example 3

4,4'-stilbene dicarboxylic acid and 2-mercapto-5-thiazolidinone were mixed at a molar ratio of 1:1.1, and then 0.2 wt% of a photoinitiator benzoin dimethyl ether (DMPA) was added in the ultraviolet Ultraviolet radiation in the instrument for 4 h gave a dicarboxylic acid compound with a hydrogen bond group on its side.

The above dicarboxylic acid compound having a hydrogen bond group, 1,6-hexanediol and trimethylolpropane are mixed at a molar ratio of 100:50:40, and then 1 wt% of a condensing agent dicyclohexylcarbodiimide (DCC) is added. And 0.5 wt% activator 4-N,N-lutidine (DMAP), reacted in DMF for 24 h, then added 6 mol% 2-MI and 5 mol% Zn(acac) ₂ and stirred for 2 h to obtain a A side hydrogen bonding group and a dynamic polymer that binds to an exchangeable ester bond.

The polymer sample has a low strength, but has a large viscosity and a very good tensile toughness, and can be stretched to a large extent without breaking (elongation at break can reach 600%). In this embodiment, the polymer can be used as an electronic packaging material or an adhesive, which can be recycled and reused during use, and the polymer sample has a long service life.

Example 4

A terminal group containing a double bond group of a hydroxyl group polybutadiene (HTPB) and a 2-tert-butoxycarbonyl aminoethanethiol as a HTPB side group double bond mole number and 2-tert-butoxycarbonylaminoethanethiol The molar ratio of fluorenyl groups is 1:1.1, and then 0.2% by weight of photoinitiator DMPA relative to 2-tert-butoxycarbonylaminoethanethiol is added. After stirring well, it is placed in an ultraviolet cross-linker for 4 hours to obtain side. A terminal hydroxyl polybutadiene having a carbamate group.

The cyclopentane-1,3-dicarboxylic acid and SOCl ₂ were mixed at a molar ratio of 1:2 and reacted in DMF to obtain a cyclopentane-1,3-diacid chloride.

The above-mentioned pendant group has a urethane group-containing HTPB, cyclopentane-1,3-diformyl chloride, isophthalic acid, glycerin mixed at a molar ratio of 40:100:40:20, and then 6 mol% 2-MI and 5 mol% Zn(acac) ₂ was reacted in dichloromethane to prepare a dynamic polymer containing a side hydrogen bond group and a bound exchangeable ester bond.

Example 5

10.8 g of cyclooctadiene and 17.2 g of m-chloroperoxybenzoic acid (mCPBA) were mixed, dissolved in 100 mL of acetonitrile, and stirred to obtain an epoxide, which was hydrolyzed in an acid solution to obtain 5-cyclooctene-1,2. -diol. Mixing 5-cyclooctene-1,2-diol and cyclooctene at a molar ratio of 1:2 in a second-generation Grubbs catalyst (1,3-bis(2,4,6-trimethylphenyl)- A 2-hydroxyl-containing polycyclooctene, that is, a polycyclooctene polyol, is obtained by the action of 2-(imidazolidine subunit)(dichlorobenzylidene)(tricyclohexylphosphine).

The above polycyclooctene polyol compound and a certain amount of 3-methyl-2-butylthioisocyanate are mixed, and triethylamine is used as a catalyst to react in dichloromethane to control the above polycyclooctene diversity in the reaction. The ratio of the number of moles of the hydroxyl group to the number of moles of isocyanate in the alcohol compound is about 10:5, and a polycyclooctene polyol having a pendant thiocarbamate group is obtained.

The polycyclooctene polyol having a thiocarbamate group and the trans-1,4-cyclohexanedicarboxylic acid having the above-mentioned pendant group are mixed according to a molar ratio of a hydroxyl group to a carboxyl group of 2:1, and then 6 mol% of 2- MI and 5 mol% Zn(acac) ₂ , a dynamic polymer containing a side hydrogen bond group and a binding exchangeable ester bond was prepared.

In this embodiment, the polymer sample can be used as a sealant or a recyclable elastic pellet, which can exhibit good toughness and elasticity, and can be pressed into products of different shapes and sizes according to needs, broken or Samples that are no longer needed can be recycled for use in new products.

Example 6

2,3-dihydroxypropyl acrylate, 5-vinyl-2-pyrrolidone, trimethylolpropane ethoxylate triacrylate molar ratio 100:15:1 mixed well, soluble in 1-butyl-3-methyl Imidazole hexafluorophosphate ([C4MIM] PF6) ionic liquid, adding 5 mol% of AIBN as initiator, then adding 6 mol% 2-MI and 5 mol% Zn(acac) ₂ , stirring well, and then pouring into a silicone pad In the glass plate mold of the sheet, ultraviolet radiation for 10 hours in an ultraviolet cross-linking instrument to obtain a dynamic polymer ionic liquid gel containing a side hydrogen bond group and a binding exchangeable ester bond.

The dynamic polymer ionic liquid gel is displaced from the ionic liquid by deionized water, and the deionized water is replaced once every 12 hours, and replaced by 5 times, thereby obtaining a side hydrogen bond group and a binding exchangeable ester bond. Dynamic polymer hydrogel.

The hydrogel prepared in this example has a modulus of 12 kPa, a strain of 12 times, and a breaking stress of 58 kPa. The organogel can be used as a cushioning packaging material for fragile items.

Example 7

The 3-isocyanate propylene and 3-hydroxy-1-propene are mixed in an equimolar ratio, and the reaction is carried out in dichloromethane with triethylamine as a catalyst to obtain a urethane group on the chain and ethylene at both ends. Base compound 7a.

Diolefin monomer compound 7a, diallyl isocyanurate and dithioerythritol, tripropyleneamine are mixed at a molar ratio of 30:20:60:1, and added to 1-butyl-3-methyl In the ionic liquid of imidazolium hexafluorophosphate ([C ₄ MIM] PF ₆ ), 0.2 wt% of benzoin dimethyl ether (DMPA) was further added, and after mixing well, 6 mol% of 2-MI and 5 mol% of Zn were added. Acac) ₂ , poured into a glass plate mold with a silica gel gasket and placed in an ultraviolet cross-linking instrument for 6 h of ultraviolet radiation to obtain a side-containing hydrogen bond group and a binding exchangeable ester bond and an exchangeable amino group. Dynamic polymer ionic liquid gel of formate linkages.

The ionic liquid gel prepared in this example has a modulus of 18 kPa, a strain of 10 times, and a breaking stress of 70 kPa. The ionic liquid gel has good stability, strong mechanical properties and excellent impact resistance, and can be used as an impact resistant protective pad.

Example 8

The ethyl 2-isocyanate and the hydroxyethyl acrylate are mixed in an equimolar ratio, and the reaction is carried out in dichloromethane with triethylamine as a catalyst to obtain a urethane group on the chain and ethylene at both ends. Base compound 8a.

The 1,4-pentadien-3-ol and cyclohexyl isocyanate are mixed in an equimolar ratio, and 1 wt% of dibutyltin dilaurate is used as a catalyst to react in dichloromethane to obtain a urethane group having a pendant group. Diolefin compound 8b.

Diolefin monomer compound 8a, diolefin monomer compound 8b, 4-(1-amino-ethyl)-seven-1,6-dien-4-ol, 1,6-hexanedithiol and 2,3 -Dithio(2-indolyl)-1-propanethiol is mixed at a molar ratio of 20:20:20:60:1, 0.2 wt% of benzoin dimethyl ether (DMPA) is added as an initiator, and then 6 mol% of TBD is added. And 5 mol% Zn(OAc) ₂ , thoroughly mixed with stirring and placed in an ultraviolet cross-linking instrument for 4 h of ultraviolet radiation, a dynamic polymerization containing a side hydrogen bond group and a bonded exchangeable ester bond, exchangeable urethane bond Things.

After the surface of the polymer material was scored with a blade, it was placed in a vacuum oven at 80 ° C for 6 hours, the scratches disappeared, and the sample was able to self-repair. The polymer material can remain soft under normal conditions and exhibits temporary rigidity upon impact, and returns to a normal flexible state after impact, and can be made into a rubber base by utilizing the stress response characteristics of the sample. The impact protection pad is used; it can also be used as a self-repairing plug for the data hole of the mobile phone.

Example 9

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 2-aminoethanethiol and 2-tert-butoxycarbonylaminoethanethiol are mixed at a ratio of a double bond group and a thiol group of 10:5:5, and 0.3 wt% of AIBN is added to obtain a reaction. A polyamine polycarbonate having a pendant group containing a urethane group.

The above-mentioned pendant group containing a urethane group-containing polyamine polycarbonate and hexamethylene diisocyanate (HDI) are mixed in an amino group and isocyanate ratio of 2:1, and then 0.2 part of silicone oil and 1.5 parts are added. The foamable polymer microspheres are placed in a container, and 8 parts of the first network polymer are added to the container and stirred uniformly; then 0.1 part of dibutyltin dilaurate and 0.1 part of triethylenediamine are added to the container, and then Add 6 mol% TBD and 5 mol% Zn(OAc) ₂ , stir rapidly by professional equipment to produce bubbles, then quickly inject into the mold, cure at room temperature for 30 min, and then cure at 80 ° C for 4 h to obtain a side containing hydrogen bond. A binary interpenetrating network composite foam having a group and a bond exchangeable urea bond.

The foam has good chemical resistance and can be used as a substitute for glass products, a rigid packaging box and a decorative sheet. It has toughness and durability, and has good biodegradability. Sex.

Example 10

The cyanuric acid and 6-chloro-1-hexene are mixed at a molar ratio of 4:1, dissolved in anhydrous dimethyl sulfoxide, and stirred under a potassium carbonate catalysis at 80 ° C for 15 h to obtain a hydrogen-containing bond group. Olefin monomer 10a.

2-hydroxyethyl acrylate, olefin monomer 10a containing hydrogen bond group, vinyl acrylate, mixed reaction at a molar ratio of 50:10:1, further adding 5 mol% of AIBN as an initiator, and then adding 6 mol% of TBD and 5 mol% Zn(OAc) ₂ , a dynamic polymer containing a side hydrogen bond group and a bonded exchangeable ester bond was prepared.

The dynamic properties of the obtained dynamic polymer: tensile strength 1.8 MPa, elongation at break 1670%; density: 110 kg/m ³ . This product has excellent impact protection and can be used for body protection, such as knee pads and neck materials for athletes.

Example 11

Allylamine, acrylamide, N,N'-methylenebisacrylamide are thoroughly mixed at a molar ratio of 50:50:10, and 5 mol% of FeCl ₃ ·6H ₂ O, 8 mol% of glycerol and 2 mol% of boric acid are added. Then, 5 mol% of AIBN was added as an initiator, and a dynamic polymer containing a side hydrogen bond group and a bound exchangeable amide bond was prepared by radical polymerization.

The dynamic polymer fluid of this structure exhibits distinct dynamic properties and "shear thickening" which can be applied to textiles or foams to make impact resistant articles, for example as sportswear or as sportswear. The mat is used.

Example 12

(1) 6-Amino-5-vinyl-2(1H)-pyrimidinone and tert-butyl acrylate were mixed at a molar ratio of 1:5, 3 mol% of AIBN was added as an initiator, and reacted for 40 min to obtain an amino group by radical polymerization. Low molecular weight copolymer of pyrimidinone and tert-butyl acrylate (molecular weight about 1600).

The copolymer of the above aminopyrimidinone and t-butyl acrylate and hexamethylene diisocyanate (HDI) are mixed at a molar ratio of amino group to isocyanate group of about 1:1 to prepare a urea skeleton-4 (1H) on the chain skeleton. A polymer of a pyrimidinone (UPy) group as a first network polymer.

(2) 2,3-Glycidyl acrylate and 3,3-dicarboxydiphenylmethane were mixed at a molar ratio of 2:1, dissolved in toluene, and heated at 60 ° C for 3 hours to prepare a diacrylate compound.

The above diacrylate compound, tert-butyl methacrylate, 2-(2-oxo-1-imidazolidinyl)ethyl methacrylic acid are mixed at a molar ratio of 10:30:10, and swelled in the first network polymer. 5 mol% of AIBN was added as an initiator, and 6 mol% of TBD and 5 mol% of Zn(OAc) _{2 were added} to prepare a pendant group containing a side hydrogen bond group, a chain skeleton containing an Upy group and a bound exchangeable ester bond. Dynamic polymer.

The obtained polymer sample has a rubbery shape and can be stretched in a wide range at a slow stretching rate to cause creep; however, if it is rapidly stretched, it exhibits an elastic characteristic and can be quickly restored by pressing with a finger. This product can be used as a toy with magical elasticity.

Example 13

Diallylaminomethoxyacetanilide, 1-(allyloxy)-3-{[3-(allyloxy)-2-hydroxypropyl]amino}propan-2-ol, dicondensation (1,2-propanediol) diacrylate, lutidine dithiol, trimethylolpropane tris(3-mercaptopropionate) mixed in a molar ratio of 20:20:20:60:1, added to 120 wt% In the plastic agent epoxy acetyl ricinoleic acid methyl ester, add 0.2wt% benzoin dimethyl ether (DMPA), mix well and mix, then add 6mol% TBD and 5mol% Zn(OAc) ₂ , pour into the silica gel In the glass plate mold of the gasket, it is placed in an ultraviolet cross-linking instrument for 8 hours of ultraviolet radiation, an epoxy acetyl ricinoleic acid containing a side hydrogen bond group and a binding exchangeable ester bond and an exchangeable urethane bond. Ester-swollen organogel.

The epoxy acetyl ricinoleic acid swelled organogel prepared in this example has a modulus of 22 kPa, a strain of 16 times, and a breaking stress of 96 kPa. This organogel can be used to prepare airborne and airborne impact resistant materials.

Example 14

(R)-3-buten-2-amine, tert-butyl-N-allyl carbamate was mixed at a molar ratio of 15:10, and 5 mol% of AIBN was added as an initiator to prepare by radical polymerization. A copolymer of both, that is, a polyamine compound having a urethane group in its pendant group.

The polyamine compound having a urethane group in the above side group and the diacetoacetyl-3,3'-dimethylbenzidine are reacted in a molar ratio of amino group to acetyl group of about 3:1, and then 6 mol% of TBD and 5 mol are added. %Zn(OAc) ₂ , a dynamic polymer containing a side hydrogen bond group and a bondable exchangeable vinyl urea bond was prepared.

The product was crushed and placed in a mold at 80 ° C for 16 h, and the sample was reshaped. It can be used as a transparent organic polymer product by utilizing properties such as plasticity, reusability, and recyclability.

Example 15

50 g of polyethylene glycol, 1.25 g of catalyst KOH were added to the reactor, and the mixture was purged with nitrogen. After heating to 120 ° C, 500 g of propylene oxide and 256 g of (S)-(oxiranemethyl)carbamic acid tert-butyl ester were respectively added. The reaction was carried out at 150 ° C for 2 h to obtain a polyether polyol having a pendant group containing a urethane group.

The above-mentioned pendant group contains a urethane group-containing polyether polyol, glycerin, and hexamethylene diisocyanate in a molar ratio of hydroxyl group to isocyanate of 125:100, and further added 0.1% by weight of dibutyltin dilaurate. And 0.05wt% triethylenediamine, then add 6mol% TBD and 5mol% Zn(OAc) ₂ , stir at a material temperature of 35 ° C at a stirring speed of 200r / min, stir rapidly by professional equipment to produce bubbles, and then quickly inject Into the mold, curing at room temperature for 30 min, and then curing at 120 ° C for 2 h, a soft foam containing a side hydrogen bond group and a bonded exchangeable urethane bond was obtained.

Performance test of the flexible foam: density (kg/m ³ ): 28; 80% compressive strength (MPa): 13; tensile strength (MPa): 4.6; elongation (%): 188; compression set Value (%): 6.8. The soft foam has good flexibility, can be stretched in a wide range, has excellent impact resistance, and can be used as an efficient shock absorbing packaging material.

Example 16

(1) undecanoic acid, bisphenol A diglycidyl ether, 1,1,1-tris(hydroxymethyl)propane triglycidyl ether are mixed at a molar ratio of 10:9:0.8, and 5 mol% of Zn (OAc) is added. ₂ as a catalyst, reacted at 100 ° C for 2 h to obtain a dynamic polymer containing a bound exchangeable ester bond as the first network polymer.

(2) Hydroxyethyl acrylate, vinyl urethane, and 1,7-octadiene are mixed at a molar ratio of 10:15:2, swelled in the first network polymer, and then added with 5 mol% of AIBN as a trigger. Further, 6 mol% of TBD was added, and the mixture was heated to 80 ° C for 8 h to obtain a dynamic polymer containing a side hydrogen bond group and a bonded exchangeable ester bond by radical polymerization.

The polymer is prepared into a film, exhibits superior comprehensive properties, has a certain tensile strength and good tear resistance, and can be stretched to a greater extent. After the polymer film was cut, the cross-section was treated in a mold at 100 ° C for 4 h, and the crack at the cross section disappeared, and the sample was re-formed to have a self-repairing function. Such dynamic polymers can be used to make functional films, or can be used as films for automobiles and furniture, or as stretch wrap films, which are scratch resistant and can be recycled and reused.

Example 17

(1) bis(cyclic carbonate), undecane-1,6,11-triamine dissolved in dichloromethane, reacted for 24 h, then heated to 90 ° C to volatilize methylene chloride, then react for 48 h, then add 6 mol %TBD and 5 mol% Zn(OAc) ₂ gave a dynamic polymer containing a bound exchangeable urethane bond as the first network polymer.

(2) Allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidinone are dissolved in toluene by molar ratio 1:1, catalyzed by potassium carbonate The tetrabutylammonium bromide is a phase transfer agent to obtain an olefin monomer 17a containing an oxazolidinone group.

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 17b containing a thiourethane group.

The olefin monomer 17a olefin monomer 17b 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 as an initiator. Free radical polymerization produces an epoxidized soybean oil-swellable dynamic polymer organogel containing a side hydrogen bond group and a bound exchangeable ester bond. This organogel can be used for cushioning pillows.

Example 18

(1) Neopentyl glycol bisacetoacetate, 2-phenyl-1,2-butanediamine, tris(2-aminoethyl)amine are mixed at a molar ratio of 100:55:33, and then 6 mol% is added. TBD and 5 mol% Zn(OAc) ₂ were heated at 110 ° C for 24 h to prepare a dynamic polymer with a bondable exchangeable vinyl urethane bond as the first network polymer.

(2) N-allyl-1H-benzimidazol-2-amine, 1-(1H-pyrrol-1-yl)-2-propen-1-one, 5-butane-2-yl-5- Prop-2-enyl-1,3-diazinon-2,4,6-trione is mixed in a molar ratio of 10:10:3, swollen in the first network polymer, and then added 5 mol% of AIBN as The initiator was heated to 80 ° C for 8 h to obtain a dynamic polymer containing a side hydrogen bond group and an exchangeable vinyl urethane bond by radical polymerization.

The mechanical properties of the dynamic polymer: tensile strength of 9.8 MPa and elongation at break of 750%. The product has good toughness and can be used to prepare polymer sealing glue, self-repairing adhesive and interlayer adhesive. Moreover, it has strong mechanical properties and excellent impact resistance, and can be used for preparing an impact resistant protective pad.

Example 19

(1) Ethyl 2-(acryloyloxy)acetate and ethyl acrylate are mixed at a molar ratio of 1:4, and 1 equivalent of AIBN is added, and heated at 60 ° C for 30 minutes to prepare a copolymer of the two, that is, a kind An acrylic oligomer containing a plurality of acetoacetates (having a molecular weight of about 1800).

The above acrylic acid oligomer containing a plurality of acetoacetates, 1,2-diphenylethylenediamine and tris(3-aminopropyl)amine have a molar ratio of acetoacetate group to amino group of about 100:120. The reaction was heated at 120 ° C for 24 h to prepare a dynamic polymer of a bondable exchangeable vinyl urethane bond as the first network polymer.

(2) mixing hydrogen-containing methyl silicone oil with a certain amount of acrylamine to control the number of moles of active hydrogen atoms (hydrogen atoms directly connected to Si) in the hydrogen-containing methyl silicone oil in the reaction and the number of moles of double bonds in the acrylamine The ratio is about 1:1, and an addition reaction is carried out using chloroplatinic acid as a catalyst to obtain a methyl silicone oil containing a polyamino group in a side group, that is, a polyorganopolyamine.

Mixing the above polyorganopolyamine with trimethylsilyl isocyanate (in a molar ratio of amino group to isocyanate of 3:2), using triethylamine as a catalyst, and reacting in dichloromethane to obtain a side group containing urea A polyorganopolyamine of a group.

The above 10 parts of the polyorganopolyamine containing a ureido group, 0.5 part of dibutyltin dilaurate, 0.1 part of triethylenediamine are swollen in the first network polymer, and 12 parts of dimethylbiphenyl diisocyanate is further added. (TODI), stirring for 24 h, gave a dynamic polymer containing a side hydrogen bond group and a binding exchangeable vinyl urethane bond, a binding exchangeable urea bond.

The obtained polymer products also have good plasticity, and can be formed into polymer film products of different shapes according to different shapes of molds, and can be applied to prepare high-performance fibers and military tents, and can be used as a film for automobiles and furniture. Scratch and can be recycled and fully utilized.

Example 20

(1) 1,10-bis(2-oxocyclohexyl)-1,10-decanedione, 1,4-butanediamine, 1,3,5-tris(aminomethyl)-2,4 The 6-triethylbenzene molar ratio was fully mixed at 100:60:32 and heated at 100 ° C for 24 h to prepare a dynamic polymer based on exchangeable vinyl amide bond as the first network polymer.

(2) mixing a certain amount of 5-cyclooctene-1,2-diol and 2-imidazolidinone-4-carboxylic acid to control the ratio of the molar ratio of the two to about 1:2, with a bicycloethyl carbon The diimine and 4-dimethylaminopyridine are used as a catalyst, and dichloromethane is used as a solvent to obtain a hydrogen bond group-containing monomer 20a.

A certain amount of hydrogen bond group-containing monomer 20a and cyclooctene are mixed and dissolved in dichloromethane, the ratio of the molar ratio of the two is controlled to be about 1:2, and the first network polymerization is added to 80 wt% of the monomer. The olefin monomer is swelled in the first network polymer, and under the action of the second generation Grubbs catalyst, a dynamic polymer containing a side hydrogen bond group and a binding exchangeable vinyl amide bond is obtained.

The polymer sample not only exhibits very good tensile toughness, but also has good plasticity and resilience; it can be prepared into different shapes according to the size of the mold, and after pressing the surface, the depression can quickly recover when the surface is When damage occurs, it can be reshaped by heating to achieve recycling. It can be made into various types of seals, or it can be used as a rubber sleeper pad fitting for rail transportation by virtue of its good shock absorption and insulation.

Example 21

(1) 3,8-diacetyldecane-2,9-dione, 4,4'-diaminodicyclohexylmethane, N,N,N,N-tetrakis(3-aminopropyl)-1 The 4-butylenediamine was mixed well at 100:60:20 and heated at 110 ° C for 24 h to prepare a dynamic polymer based on exchangeable vinyl amide bond.

(2) (17S, 18S)-18-(2-carboxyethyl)-7-ethyl-3,8,13,17,20-pentamethyl-12-vinyl-17,18-dihydro- The 2-porphyrin carboxylic acid and the tert-butyl acrylate are thoroughly mixed at a molar ratio of 10:100, fully swelled in the first network polymer, and 5 mol% of AIBN is added as an initiator to prepare a side group containing a side hydrogen. A bond group and a dynamic polymer that is exchangeable for exchange of a vinyl amide bond.

The polymer product not only exhibits excellent strength, but also exhibits excellent toughness and can be used as a sealing strip, sealing ring or elastic cushioning gasket.

Example 22

(1) The polyvinyl alcohol (average molecular weight of about 150,000) and ethyl isocyanate and 2-phenylethyl isocyanate are reacted in anhydrous dimethyl sulfoxide to maintain a molar ratio of hydroxyl group to isocyanate group of the polyvinyl alcohol of 4: 1. The molar ratio of ethyl isocyanate to 2-phenylethyl isocyanate was controlled to be 5:1 to obtain a polyvinyl alcohol having two urethane groups in the pendant group.

The above polyvinyl alcohol and suberic acid are mixed at a ratio of hydroxyl group to carboxyl group of 2:1, and then 6 mol% of TBD and 5 mol% of Zn(OAc) _{2 are added} as a catalyst to prepare a hydrogen bond group and a bondable property. A dynamic polymer that exchanges ester bonds as the first network polymer.

(2) mixing cyclohexane-3,5-dione, 3-oxa-1,5-pentanediamine, undecane-1,6,11-triamine according to a molar ratio of 100:60:30 Then, 1 part of the first network polymer is further added, the mixture is sufficiently stirred to swell the monomer in the first network polymer, and heated at 110 ° C for 24 hours to prepare a side-containing hydrogen bond group and a binding exchangeable ester bond. , a dynamic polymer that can be exchanged for insertion of a vinyl amide bond.

The product has good plasticity, can be placed in different shapes of mold according to actual needs, and under a certain temperature condition, a certain pressure can be formed according to the mold, and can be used for preparing various recyclable products. Sex crafts.

Example 23

(1) 2-[(4,4-Dimethyl-2,6-dioxocyclohexyl)methyl]-5,5-dimethylcyclohexane-1,3-dione, terminal amino group Methyl silicone oil (molecular weight about 2000), N-(2,3-diaminopropyl)-1,2,3-propane triamine mixed at a molar ratio of 100:55:33, heated at 110 ° C for 24 h, prepared A dynamic polymer of a bondable exchangeable vinyl amide bond was obtained as the first network polymer.

(2) Using hydroxyethyl acrylate as a monomer and AIBN as an initiator, the reaction was heated to 60 ° C for 2 h, and polyhydroxyethyl acrylate (molecular weight of about 2000) was obtained by free radical polymerization.

The above polyhydroxyethyl acrylate and a certain amount of ethyl isocyanate are mixed, and triethylamine is used as a catalyst to react in dichloromethane to control the ratio of the number of moles of hydroxyl group and isocyanate in the side group of polyhydroxyethyl acrylate in the reaction. It is about 10:5, so that the polyhydroxyethyl acrylate side group has a urethane group, that is, a polyol oligomer having a urethane group in a pendant group is obtained.

The above-mentioned polyol oligomer having a urethane group, 1,6-hexanediol, and isophorone diisocyanate are mixed at a molar ratio of hydroxyl group to isocyanate of 125:100, and are swollen in the first network. Add 0.1 part of dibutyltin dilaurate, 0.1 part of TBD, 0.2 part of silicone oil, 4.0 parts of foamable polymer microspheres, into the container, stir rapidly by professional equipment to produce bubbles, and then quickly inject into the mold. After curing at room temperature for 30 min and then curing at 80 ° C for 4 h, a binary interpenetrating network containing a side hydrogen bond group and a binding exchangeable urethane bond and a binding exchangeable vinyl amide bond was prepared. Composite foam.

The binary interpenetrating network composite foam material has high resilience and can be prepared as a cushion product suitable for the safety and comfort of the automobile passengers.

Example 24

(1) Mixing oligomeric polyvinyl alcohol (PVA) (molecular weight of about 600) with a certain amount of 4-acetylphenyl isocyanate, reacting with triethylamine as a catalyst in dichloromethane, and controlling PVA in the reaction. The ratio of the number of moles of hydroxyl groups to the number of moles of isocyanate is about 10:5, and a polyol oligomer having a pendant group having a urethane group is obtained.

The above-mentioned polyol group having a urethane group, 1,4-butanediol, and 1,4-cyclohexane diisocyanate are mixed at a molar ratio of hydroxyl group to isocyanate of 130:100, and then added. 0.15 wt% of dibutyltin dilaurate was prepared to obtain a dynamic polymer containing a side hydrogen bond group and a bonded exchangeable urethane bond as the first network polymer.

(2) 4,5-Dihydro-2-vinyl-1H-imidazole, 1-(3-pyrrolidinyl)-2-propen-1-one, hex-1,5-diene-3,4- The diketone is mixed at a molar ratio of 10:10:1, swollen in the first network polymer, and then added 5 mol% of AIBN as an initiator, heated to 80 ° C for 8 h, and obtained a side hydrogen by free radical polymerization. A dynamic group of bond groups and exchangeable urethane bonds.

The product exhibits good viscoelasticity, good isolation shock and stress buffering, and also exhibits excellent hydrolysis resistance. When the surface is damaged, the healing of the damaged portion can be achieved by heating to re-form, and the self-repair and recycling of the material can be realized.

Example 25

(1) Allyl piperidine-3-carbamate, hydroxypropyl methacrylate, diallyl isophthalate are mixed at a molar ratio of 50:25:1, and 6 mol% of TBD and 5 mol% of Zn are added. OAc) ₂ , by adding 5 mol% of AIBN as an initiator, a dynamic polymer containing a side hydrogen bond group and a bonded exchangeable ester bond was prepared as the first network polymer.

(2) The obtained polyhydroxyethyl acrylate (molecular weight of about 600) and a certain amount of ethyl 2-methylbutyl isothiocyanate are mixed, and triethylamine is used as a catalyst to react in dichloromethane to control the reaction. The ratio of the number of moles of hydroxyl groups in the pendant polyhydroxyethyl acrylate to the number of moles of isocyanate is about 10:7 such that the pendant polyhydroxyethyl acrylate has a thiocarbamate group.

Reaction Material A: 12 parts of the above-mentioned pendant hydroxyethyl acrylate having a thiocarbamate group, 0.5 part of 1,5-pentanediol, 0.1 part of dibutyltin dilaurate, 0.05 part of triethylenediamine , 0.1 part of TBD, 80 parts of 1-butyl-3-methylimidazolium hexafluorophosphate ([C ₄ MIM] PF ₆ ) ionic liquid and 10 parts of the first network polymer, added to the container at a temperature of 35 Stir well under the condition of stirring temperature of 200r/min; reaction material B: 10 parts of 2,6-toluene diisocyanate, added to the container, and stirred evenly at a stirring temperature of 200r/min at a temperature of 35 ° C; The reaction material A was mixed with the reaction material B, stirred for 30 minutes, and then allowed to stand for 72 hours to obtain an ionic liquid dynamic polymer gel containing a side hydrogen bond group and a binding exchangeable ester bond.

This ionic liquid gel has excellent impact protection and can be used for body protection, such as the manufacture of knee pads and neck materials for athletes.

Example 26

(1) 2,5-Dimethyl-2,4-hexadiene dicarboxylic acid and 2-mercapto-N-methylacetamide are mixed at a molar ratio of 1:1.1, and then 0.2% by weight of a photoinitiator benzoin is added. Dimethyl ether (DMPA) was irradiated with ultraviolet light for 4 h in an ultraviolet crosslinker to obtain a dicarboxylic acid compound having a hydrogen bond group on its side.

The above dicarboxylic acid compound having a hydrogen bond group, 1-benzyl-3,4-diamine pyrrolidine and pentaerythritol are mixed at a molar ratio of 100:50:30, and then 1 wt% of a condensing agent DCC and 0.5 are added. The wt% activator DMAP, reacted in DMF, gives a dynamic polymer containing a hydrogen bonding group and a binding exchangeable amide bond.

(2) N-allyl-1H-imidazole-1-carboxamide, 1-(3-buten-1-yl)-1H-1,2,4-triazole, hydroxyethyl acrylate, diene The phthalate molar ratio is 50:30:60:1, and then 5 mol% of FeCl ₃ ·6H ₂ O, 8 mol% of glycerin and 2 mol% of boric acid are added, fully swelled in the first network, and added. 5 mol% of AIBN was used as an initiator to prepare a dynamic polymer containing a hydrogen bond group and a bonded exchangeable amide bond by radical polymerization.

The obtained product has good plasticity and can be molded into polymer products of different appearances according to different shapes of the mold. The polymer sample can be made into a bend resistant hose material that can be recycled and reused after it has been damaged.

Example 27

(1) 5-(2-propenylthio)-2,4(1H,3H)-pyrimidinedione, 3-aminopropene, N,N-diallylacrylamide, hexamethylenebisacrylamide The reaction was carried out according to a molar ratio of 50:25:1:1, 7 mol% of Cu(OAc) ₂ was added, and 5 mol% of AIBN was added as an initiator to prepare a side-containing hydrogen bond group and a binding exchangeable amide bond. Dynamic polymer, as the first network polymer.

(2) 2-aminoethyl acrylate and an equimolar equivalent of acetyl bromide are dissolved in dichloromethane to obtain an amide bond-containing acrylate monomer 27a under the catalysis of triethylamine.

2-hydroxyethyl acrylate, amide bond-containing acrylate monomer 27a, 1,10-decanediol diacrylate molar ratio 100:10:3 is thoroughly mixed, swelled in the first network, and then added 5mol Using % AIBN as an initiator, a dynamic polymer containing a side hydrogen bond group and a binding exchangeable ester bond, a bonded exchangeable amide bond, was prepared.

The polymer sample has a smooth surface with a certain strength and rigidity. After being crushed and placed in a mold at 100 ° C for 8 hours, the sample can be re-formed. Polymer materials can be used in orthopedic treatment as orthopedic correction products and equipment.

Example 28

(1) N-allyl-2-aminomethylpyrrolidine, O-isobutyl-N-allylthiocarbamate mixed at a molar ratio of 15:10, and further added with 5 mol% of AIBN as a trigger A copolymer obtained by radical polymerization to obtain a polyamine compound having a thiocarbamate group on its side.

The above-mentioned pendant group has a thiocarbamate group-containing polyamine compound, 1,3-cyclopentanediamine and 2,2'-thiodiethanol diacetoacetate in a molar ratio of amino group to acetyl group. 25:10 reaction, adding 6 mol% TBD and 5 mol% Zn(OAc) ₂ to prepare a dynamic polymer containing a side hydrogen bond group and a binding exchangeable vinyl urethane bond as the first network polymerization Things.

(2) 1,6-dibromo-1,6-dideoxy-D-mannitol and sodium azide were mixed at a molar ratio of 1:4, and stirred in a DMF solution for 2 days to obtain 1,6-two. Azido-1,6-dideoxy-D-mannitol.

Mixing 1,6-diazido-1,6-dideoxy-D-mannitol and 3-(methylthio)propyl isothiocyanate in a molar ratio of 1:1.5, using triethylamine as a catalyst The reaction was carried out in dichloromethane to obtain a bis-azide compound 28a having a carbamate group on its side.

Compound 28a, 1,6-heptadiyne and cross-linking tripropargylamine were added to 1 L of DMF, and then 0.2 wt% of catalyst CuBr(PPh ₃ ) ₃ and tris[(1-benzyl-)- 1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), after being thoroughly mixed with stirring, swelled in the first network polymer, and reacted at room temperature for 12 hours under anaerobic conditions to prepare a containing side. Hydrogen bonding groups and binding exchangeable urethane linkages, dynamic polymers that are exchangeable for exchange of vinyl urethane linkages.

Example 29

(1) 1,4-pentadien-3-ol, diolefin monomer compound 29a, 4-diallylaminophenyl N-methylcarbamate, bis(2-mercaptoethyl)ether, The triacrylamide is thoroughly mixed at a molar ratio of 50:50:20:100:15, and 0.2% by weight of the photoinitiator benzoin dimethyl ether (DMPA) is added relative to the monomer, and then 6 mol% of TBD and 5 mol% of Zn (OAc) are added. ₂ , UV radiation in the UV cross-linking instrument for 8h, you can get a dynamic polymer containing a side hydrogen bond group and a binding exchangeable urethane bond, as the first network polymer.

(2) 1,4-cyclohexanedimethanol diacetoacetate, m-xylylenediamine, tris(2-aminopropyl)amine molar ratio 100:50:40 mixed thoroughly, heated at 90 ° C for 24 h A dynamic polymer containing a bound exchangeable vinyl urethane bond was prepared as the second network polymer.

(3) tert-butyl-N-allyl carbamate, methyl acrylate, tris(1,2-propanediol) diacrylate molar ratio 30:50:6 fully mixed, then add 1-but In the ionic liquid of 3-methylimidazolium hexafluorophosphate ([C ₄ MIM]PF ₆ ), fully swelled in the first network and the second network polymer, and then added 5 mol% of AIBN as an initiator, and poured into In a glass plate mold with a silica gel gasket placed in an ultraviolet cross-linking instrument for 8 hours, a side group containing a hydrogen bond group and a bonded exchangeable urethane bond were prepared, and the bond exchangeable insert was prepared. High strength ionic liquid dynamic polymer gel with ethylene urethane linkage.

The ionic liquid gel has a modulus of 36 kPa, a strain of 32 times, and a breaking stress of 200 kPa. This product can be used as a stress-carrying material in a fine mold. It has a load-bearing effect and a certain deformability. It acts as a buffer. When cracks or breakage occur, it can also be repaired by heating.

Example 30

(1) Dimerized diglyceride, 1,4-butanediamine, 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene dissolved in a molar ratio of 100:70:25 In dichloromethane, the reaction was carried out for 24 h, then heated to 90 ° C to volatilize methylene chloride, 6 mol% of TBD was added, and then reacted for 48 h to obtain a dynamic polymer containing a bound exchangeable urethane bond as the first network. polymer.

(2) 2,3-dihydroxypropyl methacrylate, styrene acrylate, tetra (ethylene glycol) diacrylate mixed at a molar ratio of 10:30:10, adding 5 mol% of AIBN as an initiator, and then adding 5 mol% Zn(OAc) ₂ , a dynamic polymer containing a bound exchangeable ester bond was prepared as the second network polymer.

(3) N-(1,1-dimethyl-3-oxobutyl)allylamide, (R)-3-buten-2-amine, N,N'-vinylbisacrylamide More than 100:50:10, fully mixed, fully swelled in the first network and the second network polymer, and then added 5 mol% of AIBN as an initiator to prepare a side containing hydrogen bond group and a binding exchangeable carbamate An ester bond, a binding exchangeable ester bond, a dynamic polymer that binds to an exchangeable amide bond.

The polymer film is tough and soft, has good strength, modulus, toughness and certain tear resistance, and exhibits excellent properties especially in terms of tensile toughness. The sample was recovered after being pulled off, and after being placed in a mold at 90 ° C for 3 hours, it was re-formed and reused, and it can be used as a film for automobiles and furniture, or a stretchable packaging film.

Example 31

4-Amino-3,5-difluorophenylethyl ester 1.0 g, potassium permanganate 8.5 g, 8.6 g of ferrous sulfate heptahydrate, dissolved in 30 ml of LDCM, refluxed overnight to give the azobenzene product. 0.81 g of the above azobenzene product, 4.8 g of 1,6-hexanediol and 0.03 g of K ₂ CO ₃ were dissolved in 14 mL of DMSO and reacted at 60 ° C for 9 hours to obtain a terminal hydroxybenzene-containing azobenzene. 0.72 g of the above-mentioned hydroxyl group-containing azobenzene was added, 1.84 mL of triethylamine, 3 mg of DMAP was dissolved in 5 mL of anhydrous DCM, and 0.6 mL of methacryloyl chloride was added thereto, and the reaction was continued overnight to obtain a diene azobenzene 31a.

Polymethylhydrogensiloxane (PHMS, molecular weight 8000), 2-(2-oxo-1-imidazolidinyl)ethyl methacrylic acid, hydroxyethyl acrylate, azobenzene 31a of the above diene according to molar ratio 1 :40:60:15 mixed, dissolved in dichloromethane, added 6mol% TBD and 5mol% Zn(OAc) ₂ , then added 0.1wt% Pt(cod)Cl ₂ , reacted at 70 ° C for 24h, to obtain a kind A dynamic polymer containing a side hydrogen bond group and a bound exchangeable ester bond.

The dynamic polymer can be used to make a coating that is applied to the surface of the substrate to dry to form a scratch-resistant, peelable, recyclable coating.

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 polymer having a hybrid crosslinked network, characterized in that it comprises covalent crosslinks and supramolecular hydrogen bond crosslinks, and covalent crosslinks reach a covalently crosslinked gel point in at least one network structure Above; the covalently crosslinked network backbone chain comprises at least one bound exchangeable covalent bond, and the bond exchangeable covalent bond is a necessary condition for forming or maintaining a covalent crosslinked structure of the dynamic polymer; Containing a nucleophilic group for carrying out a binding exchangeable covalent bond exchange reaction; the hydrogen bond cross-linking is formed by a side hydrogen bond group present on a side chain, a side chain or a side group and a side chain of the polymer chain The dynamic polymer has a composition comprising a catalyst for performing a bondable exchangeable covalent exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
According to one of the claim 1 having a hybrid dynamic crosslinked network polymer, wherein, R 1, R 2 are each independently selected from a hydrogen atom, a halogen atom, C 1-20 hydrocarbyl, C 1-20 a heterohydrocarbyl group, a substituted C 1-20 hydrocarbyl group, a substituted heterohydrocarbyl group; R 3 is selected from a hydrogen atom, a C 1-20 hydrocarbyl group, a C 1-20 heterohydrocarbyl group, a substituted C 1-20 hydrocarbyl group, a substituted heterohydrocarbyl group; It is 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.
A dynamic polymer having a hybrid crosslinked network according to claim 1 wherein said combination The exchangeable covalent bond group is selected from the group consisting of an ester group, a thioester group, a carbonate group, an amide group, a urethane group, a thiocarbamate group, a urea group, a vinyl amide group, and a vinyl amide group. An acid ester group and a derivative thereof.
The dynamic polymer having a hybrid crosslinked network according to claim 1, wherein the side group or the side chain or the side group and the side chain of the hybrid crosslinked network further comprise at least one of the following A nucleophilic group that undergoes a binding exchangeable covalent bond exchange reaction: a hydroxyl group, a thiol group, an amino group.
The dynamic polymer having a hybrid crosslinked network according to claim 1, wherein the catalyst for the transesterification reaction is selected from the group consisting of acids and acid salts thereof, alkali metal of Group IA and compounds thereof, Group IIA alkali metal and its compound, aluminum metal and compound thereof, tin compound, group IVB element compound, anionic layer column compound, supported solid catalyst, organozinc compound, organic compound;

The catalyst for the amine exchange reaction is selected from the group consisting of aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzyl Hydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N,N'-diphenyl thiourea, bismuth trifluoromethanesulfonate, montmorillonite, ruthenium tetrachloride, Glutamine transaminase, divalent copper compound, trivalent iron compound.
A dynamic polymer having a hybrid crosslinked network according to claim 1, wherein the network of the covalently crosslinked network contains a plurality of segments between each of the two covalent crosslinking points At 0.1 of the side hydrogen bond groups.
A dynamic polymer having a hybrid crosslinked network according to claim 1 wherein a backbone hydrogen bonding group is further present.
A dynamic polymer having a hybrid crosslinked network according to claim 1, wherein a carboxyl group, a fluorine group, a hydroxyl group, an amino group or a fluorenyl group group for forming a hydrogen bond is further present.
A dynamic polymer having a hybrid crosslinked network according to any one of claims 1-8, wherein the state of the dynamic polymer is selected from the group consisting of solid polymers, ionic liquid gels, and oligomers. Gel, plasticizer swollen gel, organogel, hydrogel, foam.
The dynamic polymer having a hybrid crosslinked network according to claim 1, wherein the raw material component constituting the dynamic polymer further comprises any one or any of the following additives: additives, additives ,filler.
The dynamic polymer having a hybrid crosslinked network according to claim 1 or 10, wherein the additive and the additive which can be added are selected from any one or more of the following: solvent, catalyst, initiator , antioxidants, light stabilizers, heat stabilizers, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, Matting agent, flame retardant, bactericidal fungicide, dehydrating agent, nucleating agent, rheological agent, thickener, thixotropic agent, leveling agent, chain extender, foam stabilizer, foaming agent; The filler is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
A dynamic polymer having a hybrid crosslinked network, characterized in that it comprises covalent cross-linking and supramolecular hydrogen Key cross-linking, covalent cross-linking reaches at least one network structure above the gel point of covalent cross-linking; the covalent cross-linking network backbone chain comprises at least one binding exchangeable covalent bond, the combination a sexually exchangeable covalent bond is a prerequisite for forming or maintaining a covalent cross-linking structure of a dynamic polymer; it contains a nucleophilic group for carrying out a binding exchangeable covalent bond exchange reaction; the hydrogen bond cross-linking is present Forming at a side of the polymer chain, at least one side hydrogen bond group in the side chain, and a skeleton hydrogen bond group on the polymer chain skeleton; the composition thereof is used for performing a bond exchangeable covalent bond exchange reaction The required catalyst;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, wherein there is only one crosslinked network, and covalent crosslinking in the network reaches above a gel point; wherein the covalently crosslinked network chain skeleton contains at least a binding exchangeable covalent bond which is necessary for the formation or maintenance of a covalent cross-linking structure of a dynamic polymer; it contains a nucleophilic group for performing a bond exchangeable covalent bond exchange reaction; a polymer chain The side hydrogen bond groups are present on the pendant, side or side groups and side chains of the backbone; the composition of which contains the catalyst required for the exchangeable exchangeable covalent bond exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, characterized in that the dynamic polymer is composed of two crosslinked networks, wherein the covalent crosslink in the first network reaches a gel point above the covalent crosslink, Wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming or maintaining a covalent cross-linking structure of the dynamic polymer; a nucleophilic group of a valency exchange reaction; the side group and the side chain do not contain the side hydrogen bond group; the second network does not contain covalent crosslinks, but the side chain, side chain of the polymer chain or a side hydrogen bonding group is present on the side group and the side chain; the composition thereof contains a catalyst required for carrying out the combined exchangeable covalent bond exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, characterized in that the dynamic polymer is composed of two networks, wherein the covalent cross-linking in the first network reaches a gel point above the covalent cross-linking, wherein The covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming or maintaining a covalent cross-linking structure of a dynamic polymer; it contains a bond for exchangeable covalent bond a nucleophilic group exchanging the reaction; the side group and the side chain do not contain the side hydrogen bond group; the covalent crosslink in the second network reaches a gel point above the covalent crosslink, wherein the total The crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming or maintaining a covalent cross-linking structure of the dynamic polymer; and contains a bond exchangeable covalent bond exchange reaction a nucleophilic group; the side group, the side chain or the side group and the side chain having the side hydrogen bond group; and the composition thereof contains a catalyst required for performing a bond exchangeable covalent bond exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, characterized in that the dynamic polymer is composed of two networks, wherein the covalent cross-linking in the first network reaches a gel point above the covalent cross-linking, wherein The covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming or maintaining a covalent cross-linking structure of a dynamic polymer; it contains a bond for exchangeable covalent bond a nucleophilic group that exchanges the reaction; the side group, the side chain or the side group and the side chain contain the side hydrogen bond group; the second network does not contain covalent crosslinks, but its side group, side chain or side The side and side chains contain the side hydrogen bond group; the composition of which contains the catalyst required for the bond exchangeable covalent bond exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, characterized in that the dynamic polymer is composed of two networks, wherein the covalent cross-linking in the first network and the second network reaches a covalently crosslinked gel Above, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, which is a necessary condition for forming or maintaining a dynamic polymer covalently crosslinked structure; a nucleophilic group capable of exchanging a covalent bond exchange reaction; the pendant hydrogen bond group is contained on a side group, a side chain or a side group and a side chain; the first and second networks are different; Containing a catalyst for carrying out a combined exchangeable covalent bond exchange reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network, characterized in that the dynamic polymer is composed of three networks, wherein the covalent cross-linking in the first network reaches a gel point above the covalent cross-linking, wherein The covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond crosslink, which is a necessary condition for forming or maintaining a covalent crosslinked structure of the dynamic polymer; a nucleophilic group of a valency exchange reaction; but without the side hydrogen bonding group; the second network does not contain covalent crosslinks, but the pendant, side or side groups and side chains of the polymer chain There is a side hydrogen bonding group; the covalent crosslinking in the third network reaches above a gel point of covalent crosslinking, wherein the covalently crosslinked network chain backbone contains at least one bound exchangeable covalent bond, It is a necessary condition for forming or maintaining a covalent cross-linking structure of a dynamic polymer; the side group, the side chain or the side group and the side chain contain the side hydrogen bond group; and it contains a covalent exchangeable covalent bond a nucleophilic group of a bond exchange reaction; the composition of which contains The catalyst of exchangeable key exchange covalently desired reaction;

Wherein the binding exchangeable covalent bond comprises at least one of the structures represented by the following formula:

Wherein X is selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom; Y is selected from the group consisting of an oxygen atom, a sulfur atom and an NH group; and Z is selected from an oxygen atom and a sulfur atom;

When X is O or S, R 1 and R 2 are absent;

When X is N, R 1 is present, R 2 is absent; and R 1 is selected from a hydrogen atom, a substituted atom, and a substituent;

When X is C, Si, R 1 and R 2 are present, and R 1 and R 2 are each independently selected from a hydrogen atom, a substituted atom, a substituent; wherein R 1 and R 2 are the same or different;

Wherein the side hydrogen bond group contains both a hydrogen bond acceptor and a hydrogen bond donor;

Wherein the hydrogen bond acceptor contains 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 CR group; wherein R is selected from a hydrogen atom, a substituted atom, and a substituent;

Wherein the hydrogen bond donor comprises a structure represented by the following formula:
A dynamic polymer having a hybrid crosslinked network according to any one of claims 1-8, 12-18, which is applied to the following materials or articles: shock absorbers, cushioning materials, impact resistant materials, sports Protective products, military and police protective products, self-healing coatings, self-healing sheets, self-healing adhesives, self-healing sealing materials, interlayer adhesives, ductile materials, self-adhesive toys, shape memory materials.