CN109206550B

CN109206550B - Hybrid supermolecule dynamic polymer

Info

Publication number: CN109206550B
Application number: CN201710524135.1A
Authority: CN
Inventors: 不公告发明人
Original assignee: Xiamen Tiance Material Technology Co ltd
Current assignee: Xiamen Iron Cloth Mstar Technology Ltd
Priority date: 2017-06-30
Filing date: 2017-06-30
Publication date: 2022-09-09
Anticipated expiration: 2037-06-30
Also published as: CN109206550A

Abstract

The invention discloses a hybrid supramolecular-action dynamic polymer, which contains a dynamic polymer with metal-ligand action and supramolecular hydrogen bond action formed by participation of hydrogen bond groups on side groups. The metal-ligand action has the advantages of abundant formation modes, dynamic reversibility, directional recognition and the like, and the dynamic polymer has self-repairing property, reusability and recyclability by virtue of the dynamic reversibility of the metal-ligand action and the supermolecule hydrogen bond action. The dynamic polymer can be widely applied as a self-repairing material, a tough material, a sealing material, an adhesive, a force sensor material and the like.

Description

Hybrid supramolecular-acting dynamic polymer

The technical field is as follows:

the invention relates to the field of intelligent materials, in particular to a hybrid supramolecular interaction dynamic polymer containing metal-ligand interaction and supramolecular hydrogen bond interaction formed by participation of side group hydrogen bond groups

Background

The supermolecule polymer is a brand new field in the high molecular science research, and the dynamic polymer based on the supermolecule effect has the molecular structure stability of the traditional covalent polymer and the dynamic reversibility of the supermolecule polymer, and is a brand new intelligent material. Compared with dynamic covalent bonds, the acting force of the supermolecule action is small, the required dynamic conditions are mild, the dynamic performance is good, and the supermolecule dynamic covalent bonds play an important role in the aspects of building functional molecules and materials, developing chemical sensors, regulating and controlling biomolecules, controlling intelligent molecular switches and machines and the like.

The types of supramolecular actions discovered at present are more and more abundant, and reports on dynamic polymers formed by supramolecular actions are more and more, and mainly focus on that each dynamic polymer only contains one supramolecular action to provide the dynamic property of the polymer, but due to the limited dynamic property of single supramolecular action, the synergistic and orthogonal comprehensive properties are difficult to form. In order to obtain dynamic polymers with diversity and synergistic orthogonal dynamics, a new supramolecular interaction composition mode needs to be developed to solve the defects existing in the existing dynamic polymers.

Disclosure of Invention

Against this background, the present invention provides a hybrid supramolecular-acting dynamic polymer comprising a metal-ligand interaction and supramolecular hydrogen bonding interactions formed by participation of pendant hydrogen bonding groups. The hybrid supermolecule action dynamic polymer has good stability, can have good dynamic reversibility under general mild conditions, and can embody self-repairability, reusability, recoverability and bionic mechanical property.

The invention is realized by the following technical scheme:

the invention relates to a hybrid supramolecular-action dynamic polymer, which contains metal-ligand action and supramolecular hydrogen bond action formed by participation of side group hydrogen bond groups; wherein the metal-ligand interaction is achieved by the interaction of ligand groups contained in the dynamic polymer structure with the introduced metal center; wherein at least one of the polymer chain skeleton, the side group and the end group of the dynamic polymer contains a ligand group.

In an embodiment of the present invention, the hybrid supramolecular interaction dynamic polymer further comprises at least one of backbone hydrogen bonding groups and terminal hydrogen bonding groups.

In an embodiment of the invention, the hybrid supramolecular acting dynamic polymer and its composition and polymer chain topology in the starting components are selected from the group consisting of linear, cyclic, branched, clustered, cross-linked and combinations thereof.

According to a preferred embodiment of the invention, the dynamic polymer is a non-crosslinked structure, wherein the degree of crosslinking for metal-ligand interactions is below its gel point, the degree of crosslinking for supramolecular hydrogen bonding interactions is below its gel point, and the sum of the two degrees of crosslinking is below the gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

According to another preferred embodiment of the present invention, the dynamic polymer is a crosslinked structure in which the degree of crosslinking by metal-ligand interaction is below its gel point, the degree of crosslinking by supramolecular hydrogen bonding is below its gel point, and the sum of the degrees of crosslinking is above the gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

According to another preferred embodiment of the invention, the dynamic polymer is a crosslinked structure, wherein the degree of crosslinking for metal-ligand interactions is below its gel point and the degree of crosslinking for supramolecular hydrogen bonding interactions is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

According to another preferred embodiment of the invention, the dynamic polymer is a crosslinked structure, wherein the degree of crosslinking for metal-ligand interactions is above its gel point and the degree of crosslinking for supramolecular hydrogen bonding interactions is below its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

According to another preferred embodiment of the invention, it is characterized in that the dynamic polymer is a crosslinked structure in which the degree of crosslinking for the metal-ligand interaction is above its gel point and the degree of crosslinking for the supramolecular hydrogen bonding is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

In an embodiment of the invention, the ligand group (represented by L) is selected from cyclopentadiene or a structural unit containing at least one coordinating atom (represented by a). A coordinating atom may form one or more coordination bonds to one or more metal centers (including, but not limited to, metal ions, metal centers of metal chelates, metal centers of metal organic compounds, metal centers of metal inorganic compounds, represented by M), and a metal center may also form one or more coordination bonds to one or more coordinating atoms. The number of coordination bonds formed by a ligand group and a metal center is called the number of teeth of the ligand group, in the embodiment of the present invention, in the same system, a metal center can form a metal-ligand action with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring by connecting through the metal center, so that the present invention can effectively provide dynamic metal-ligand actions with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:

wherein A is a coordinating atom and M is in a metalA core, wherein an A-M bond formed by each ligand group and the metal core is a tooth, wherein the bonding of A to A represents that the coordinating atoms belong to the same ligand group, and when two or more coordinating atoms are contained in a ligand group, A may be the same atom or different atoms selected from the group consisting of but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. Incidentally, sometimes a exists in the form of negative ions;

is a cyclopentadiene ligand. In the present invention, it is preferable that one coordinating atom form only one coordination bond with one metal center, and therefore the number of coordinating atoms contained in a ligand group is the number of teeth of the ligand group. The ligand group interacts with the metal-ligand formed by the metal center (as M-L) _x Representing the number of ligand groups interacting with the same metal center) is related to the type and number of coordinating atoms on the ligand groups, the type and valence of the metal center, and the ion pair.

The metal centre M may be the metal centre of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.

In an embodiment of the present invention, the pendant hydrogen bonding group participating in the formation of supramolecular hydrogen bonding preferably comprises at least one of the structures represented by the following general formulas:

wherein X is selected from oxygen atom, sulfur atom, silicon atom and nitrogen atom, and Y is selected from oxygen atom and sulfur atom; a is R attached to the X atom ₂ The number of (2); when X is an oxygen atom or a sulfur atom, a is 0, R ₂ Is absent; when X is selected from nitrogen atoms, a ═ 1; when X is a silicon atom, a ═ 2; r is ₁ 、R ₂ Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbyl groups having a molecular weight of no more than 1000 Da; j is a divalent linking group selected from the group consisting of single bonds, heteroatom linkers, divalent small molecule hydrocarbon groups having a molecular weight of no more than 1000 Da; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group having a molecular weight not exceeding 1000 Da;

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain (including multilevel structures thereof), or any other suitable group/atom; wherein, J, R ₁ 、R ₂ And any two or more of Q may be linked together to form a ring, the ring includes but is not limited to aliphatic rings, aromatic rings, ether rings, condensed rings and combinations thereof, the ring-forming atoms of the ring structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on each ring-forming atom may or may not be substituted.

In an embodiment of the present invention, the dynamic polymer further comprises supramolecular hydrogen bonding in which at least one of a backbone hydrogen bonding group and a terminal hydrogen bonding group participates.

In the present invention, the backbone hydrogen bonding group refers to a hydrogen bonding group which is located on the backbone of the non-crosslinked polymer chain and the backbone of the dynamically crosslinked polymer network chain, and in which at least a part of the atoms are part of the chain backbone, and which preferably contains the following structural elements:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein,

refers to the linkage to the backbone of the polymer chain, the backbone of the cross-linked network chain.

In the present invention, the terminal hydrogen bonding group may be any suitable hydrogen bonding group.

In the embodiment of the invention, the hybrid supramolecular interaction dynamic polymer and the composition thereof can be in the forms of solution, emulsion, common solid, paste, glue, elastomer, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel), foam material and the like.

In an embodiment of the present invention, the hybrid supramolecular interaction dynamic polymer is formed by raw material components which further comprise any one or more of the following additives: other polymers, auxiliaries, fillers;

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

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

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

In an embodiment of the invention, the hybrid supramolecular interaction dynamic polymer can be applied to the following materials or products: the material comprises a self-repairing coating, a self-repairing plate, a self-repairing adhesive, a sealing material, a tough material, an adhesive, a toy material, an energy storage device material, a force sensor material and a shape memory material.

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

(1) according to the invention, the dynamic polymer is constructed by taking the metal-ligand effect and the supramolecular hydrogen bond effect as dynamic reversible bonds, the dynamic properties of the metal-ligand effect and the supramolecular hydrogen bond effect and the orthogonality and the cooperativity of the metal-ligand effect and the supramolecular hydrogen bond effect are fully utilized, the dynamic polymer with the characteristics of quick self-repairing and recycling is obtained, and the material can be endowed with excellent self-repairing property at normal temperature or other use temperatures; the metal-ligand action and the supermolecule hydrogen bond action can be sequentially broken in a mode of 'sacrificial bonds' under the action of external force, and excellent tensile toughness and tear resistance are provided for the cross-linked polymer. Meanwhile, because no common covalent crosslinking above the gel point exists, the polymer material can realize self-repairing, shaping, recycling and reprocessing to a greater extent, so that the polymer material has a wider application range and a longer service life.

(2) The hybrid supramolecular-acting dynamic polymer has good controllability. By controlling parameters such as ligand groups, metal centers and the like, dynamic polymers with different structures, different apparent characteristics, adjustable performance and wide application can be prepared. Meanwhile, because the hydrogen bond groups of the side groups have structural diversity, the dynamic property of the polymer can be combined, matched and regulated in a wider range by controlling the types and the number of the hydrogen bond groups of the side groups, and based on the difference of the dynamic property of the polymer and the dynamic property of the metal-ligand groups, the polymer material with richer structure, more diverse performance and more hierarchical dynamic reversible effect can be obtained.

(3) In the invention, because the hydrogen bond group of the side group is positioned on the side group of the polymer chain, the movement of the group and the chain is more free, the dynamic property is stronger, and the self-repairing is particularly beneficial to be carried out. The side group hydrogen bond group in the invention is preferably a group based on (thio) carbamate/urea unit, on one hand, the hydrogen bond with good dynamic property is particularly suitable for forming, on the other hand, the hydrogen bond is relatively hydrolysis-resistant, and the preparation is relatively convenient. This is not comparable to other hydrogen bonding systems.

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

Detailed Description

The invention relates to a hybrid supramolecular-action dynamic polymer, which contains metal-ligand action and hydrogen bond action formed by participation of side group hydrogen bond groups; once the metal-ligand interactions and hydrogen bonding interactions contained in the dynamic polymer are dissociated, the polymer system decomposes into any one or more of the following subunits: polymer chain fragments, polymer clusters, etc.; meanwhile, the mutual transformation and dynamic reversibility between the dynamic polymer and the units can be realized through the interaction and dissociation of metal-ligand interaction and hydrogen bond interaction.

In an embodiment of the present invention, the dynamic polymer further comprises at least one of a backbone hydrogen bonding group and a terminal hydrogen bonding group.

The term "polymerization" reaction/action as used in the present invention refers to a chain extension process/action in which a lower molecular weight reactant forms a product having a higher molecular weight by a polycondensation, polyaddition, ring-opening polymerization, or the like reaction. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The "polymerization" referred to in the present invention includes a linear growth process, a branching process, a ring formation process, a crosslinking process, and the like of a reactant molecular chain; in embodiments of the invention, "polymerization" includes chain growth processes resulting from covalent bonding and non-covalent interactions of metal-ligand interactions and hydrogen bonding.

The term "cross-linking" reaction/action as used in the present invention refers to the process of chemical linkage between reactant molecules and/or covalent bonds within reactant molecules, as well as the physical action of metal-ligand interactions and/or supramolecular hydrogen bonding interactions, to form a product having a three-dimensional infinite network type. In the crosslinking process, a polymer chain generally grows in a two-dimensional/three-dimensional direction to gradually form a two-dimensional or three-dimensional cluster, and then develops into a three-dimensional infinite network structure. The crosslinked structure in the present invention means a three-dimensional infinite network structure having a gel point or more (including a gel point, the same applies hereinafter), and the uncrosslinked structure means a linear, cyclic, branched or the like structure and a two-dimensional or three-dimensional cluster structure having a gel point or less. The "gel point" (also called percolation threshold) in the present invention refers to the reaction point at which the reactants undergo a sudden increase in viscosity during crosslinking, begin to gel, and first begin to crosslink to a three-dimensional infinite network. The crosslinked product above the gel point (including the gel point) has a three-dimensional infinite network structure, the crosslinked network forms a whole and spans the whole polymer structure, and the crosslinked structure is relatively stable and firm; the crosslinked product, which is below the gel point, does not form a three-dimensional infinite network structure and does not belong to a crosslinked network that can be integrated across the entire polymer structure. When multiple cross-linking is present, the cross-linking may be above or below its gel point. In this patent, the cross-linking referred to is in particular supramolecular cross-linking, if not specified otherwise.

The dynamic polymer has a polymer chain topology selected from the group consisting of, but not limited to, linear, cyclic, branched, clustered, cross-linked, and combinations thereof; the composition thereof and the chain topology of the polymer in the feedstock may also be selected from the group including, but not limited to, linear, cyclic, branched, clustered, crosslinked, and combinations thereof.

Wherein, the linear structure means that the polymer molecular chain is in a regular or irregular long-chain linear shape and is generally formed by connecting a plurality of repeating units on a continuous length, and the side group in the polymer molecular chain generally does not exist in a branched chain; for "linear structures," they are generally formed by polymerization of monomers that do not contain long chain pendant groups by polycondensation, addition polymerization, or ring opening.

Wherein, the "cyclic" structure refers to that the polymer molecular chain exists in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple rings, bridged ring, nested ring, etc.; as the "cyclic structure", it can be formed by intramolecular and/or intermolecular cyclization of a linear or branched polymer, and can also be produced by ring-expanding polymerization or the like.

Wherein, the "branched" structure refers to a structure containing side chains, branched chains, and branched chains on the polymer molecular chain, including but not limited to star, H, comb, dendritic, hyperbranched, and combinations thereof, and further combinations thereof with linear and cyclic structures, such as a linear chain end connected to a cyclic structure, a cyclic structure combined with a comb, a dendritic chain end connected to a cyclic chain, and the like; for "side chains, branches and forked chains of the polymer" it may have a multistage structure, for example, it may be possible to continue with one or more stages of branching on the branches of the polymer molecular chain. As to the "branched structure", the preparation method thereof is so many, and is generally well known to those skilled in the art, and it can be formed, for example, by polycondensation of a monomer having a long-chain pendant group, or by chain transfer reaction of a radical during addition polymerization, or by extending a branched structure on a linear molecular chain by radiation and chemical reaction. The branched structure is further subjected to intramolecular and/or intermolecular reaction (crosslinking) to produce a cluster and a crosslinked structure.

The "cluster" structure refers to a two-dimensional/three-dimensional structure below the gel point, which is generated by intramolecular and/or intermolecular reaction of polymer chains.

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

In the embodiment of the present invention, the dynamic polymer, the composition thereof, and the raw material components may have only one topological form of the polymer, or may be a mixture of polymers having a plurality of topological forms.

In embodiments of the present invention, the ligand groups (denoted by L) include, but are not limited to, ligand groups on the backbone of the polymer chain (hereinafter "backbone ligands") as well as ligand groups on pendant groups of the polymer chain (hereinafter "pendant ligands") and ligands at the end of the polymer chain as well as other compounds (hereinafter "end ligands"). The skeleton ligand refers to that at least two atoms in the group directly participate in the construction of the polymer chain skeleton, including the skeleton of a non-covalent cross-linked polymer main chain, a side chain, a branched chain and a branched chain, preferably the skeleton of a non-covalent cross-linked network chain; the side group ligand means that all atoms on the group are on the side group; the terminal ligand means that all atoms on the group are terminal. In some cases, the terminal ligands are also pendant or backbone ligands. The ligand groups may be generated during the polymerization/crosslinking of the polymer, or may be generated in advance and then polymerized/crosslinked, preferably generated in advance. It should be noted that in addition to the above ligand groups, the polymers of the present invention may also contain other ligand groups having only one atom involved in the building up of the backbone of the polymer chain.

In embodiments of the present invention, wherein one or more of the same or different ligand groups may be present on the same molecular chain. The metal-ligand effect is formed by at least one ligand group in polymer skeleton ligand, side group ligand, end group ligand and the like and the introduced metal center; and any ligand groups may, under certain conditions, form inter-chain interactions which produce polymerization and/or cross-linking, and/or intra-chain metal-ligand interactions which generally do not produce cross-linking; furthermore, it is not excluded that grafting may occur.

In the present invention, the term "polymer main chain" refers to a chain having the largest number of links in a polymer structure, unless otherwise specified. The side chain refers to a chain structure which is connected with a polymer main chain skeleton/a crosslinking network chain skeleton in a polymer structure and is distributed beside the skeleton, and the molecular weight of the chain structure exceeds 1000 Da; wherein the branched chain and the branched chain refer to chain structures which are branched from a polymer main chain skeleton/a crosslinking network chain skeleton or any other chains and have the molecular weight of more than 1000 Da; for simplicity, side chains, branches, and branched chains are collectively referred to as side chains unless otherwise specified, when the molecular weight exceeds 1000 Da. The "side group" refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with the polymer main chain skeleton/crosslinking network chain skeleton and distributed beside the main chain skeleton in the polymer structure. For the side chain and the side group, the side chain and the side group can have a multi-stage structure, that is, the side chain can be continuously provided with the side group and the side chain, the side chain of the side chain can be continuously provided with the side group and the side chain, and the side chain also comprises chain structures such as branched chain and branched chain. The "terminal group" refers to a chemical group which is linked to the polymer chain skeleton in the polymer structure and is located at the end of the chain skeleton; in the present invention, the side groups may have terminal groups in specific cases.

In the present invention, the pendant hydrogen bonding groups participate in the formation of hydrogen bonding interactions, which are formed by hydrogen bonding groups (pendant hydrogen bonding groups) present on the pendant groups of the polymer chains in the dynamic polymer and its composition; it can be formed between the hydrogen bonds of the side groups, and can also be formed between the hydrogen bonds of the side groups and the hydrogen bonds of other positions such as skeleton hydrogen bond groups, end group hydrogen bond groups and the like. The backbone hydrogen bonding group wherein at least a portion of the atoms are part of a chain backbone; the terminal hydrogen bonding group, wherein at least part of the atoms are the terminal group of the polymer chain or the constituent of the terminal group of the small molecule. In the invention, hydrogen bonds can be selectively formed between any hydrogen bond groups at other positions such as skeleton hydrogen bond groups, terminal hydrogen bond groups and the like; other components present in the dynamic polymer composition including, but not limited to, hydrogen bonding groups in small molecules, polymers, fillers, may also selectively participate in hydrogen bonding. The hydrogen bonding, under certain conditions, may form inter-chain interactions that produce polymerization and/or cross-linking, and/or intra-chain interactions that generally do not produce cross-linking; furthermore, it is not excluded that grafting may occur.

The ligand groups and hydrogen bonding groups described in the present invention may be on the same polymer or on different polymers. When on different polymers, the dynamic polymer is a polymer composition in which at least one polymer component contains only ligand groups and the pendant hydrogen bonding groups are present in the other polymer component. In the present invention, when a plurality of polymer components are present, the components may be compatible or incompatible with each other; the different components may be dispersed, interspersed or partially interspersed, but the invention is not limited in this regard.

In the present invention, for a dynamic polymer having a crosslinked structure, which constitutes dynamic supramolecular crosslinks by metal-ligand action and/or hydrogen bond action, the sum of the degrees of crosslinking of the dynamic supramolecular crosslinks is preferably above its gel point; however, the degree of crosslinking by both the metal-ligand interaction and the hydrogen bonding interaction may be at least the gel point or less.

According to a preferred embodiment of the invention, the dynamic polymer is a non-crosslinked structure, wherein the degree of crosslinking of the metal-ligand interaction is below its gel point, the degree of crosslinking of the supramolecular hydrogen bonding interaction is below its gel point, and the sum of the degrees of crosslinking of the two is below the gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action. In this embodiment, the crosslinking degree of dynamic supramolecular crosslinks and the crosslinking degree of supramolecular hydrogen bond crosslinks formed due to the metal-ligand action and the sum thereof are both below the gel point, enabling to obtain a polymer with fast self-repair, recyclable and reusable properties and good processability, and which is easy to recycle and reuse.

According to another preferred embodiment of the present invention, the dynamic polymer is a crosslinked structure in which the degree of crosslinking by metal-ligand interaction is below its gel point, the degree of crosslinking by supramolecular hydrogen bonding is below its gel point, and the sum of the degrees of crosslinking is above the gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action. In the embodiment, the crosslinking degree of dynamic supramolecular crosslinking and the crosslinking degree of supramolecular hydrogen bonding crosslinking formed under the action of the metal-ligand are below the gel point, and the sum of the crosslinking degree and the crosslinking degree is above the gel point, so that viscoelastic transformation can be realized under stress/strain response, and the strength of the material is improved.

According to another preferred embodiment of the invention, the dynamic polymer is a crosslinked structure, wherein the degree of crosslinking for metal-ligand interactions is below its gel point and the degree of crosslinking for supramolecular hydrogen bonding interactions is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action. In the embodiment, the crosslinking degree of the dynamic supermolecule crosslinking formed by the metal-ligand action is below the gel point, so that the characteristics of quick self-repairing, recycling and reuse and the like can be obtained; and the crosslinking degree of the supermolecule hydrogen bond crosslinking is higher than the gel point, so that the viscoelasticity or the balance structure of the material matrix is favorably supplemented.

According to another preferred embodiment of the present invention, the dynamic polymer is a crosslinked structure in which the degree of crosslinking for metal-ligand interaction is above its gel point and the degree of crosslinking for supramolecular hydrogen bonding is below its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action. In the embodiment, the crosslinking degree of the dynamic supermolecule crosslinking formed under the action of the metal-ligand is higher than the gel point, so that viscoelastic transformation can be realized under stress/strain response, and the strength of the material is improved; and the crosslinking degree of the supramolecular hydrogen bond crosslinking is below the gel point, so that the material is beneficial to supplementing the rapid self-repairing and processing performances.

According to another preferred embodiment of the invention, it is characterized in that the dynamic polymer is a crosslinked structure, wherein the degree of crosslinking for metal-ligand interactions is above its gel point and the degree of crosslinking for supramolecular hydrogen bonding interactions is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action. In the embodiment, the crosslinking degree of dynamic supramolecular crosslinking formed under the action of the metal-ligand is higher than the gel point of the dynamic supramolecular crosslinking, so that viscoelastic transformation can be realized under stress/strain response, and the strength of the material is improved; and the crosslinking degree of the supermolecule hydrogen bond crosslinking is higher than the gel point, so that the strength and viscoelasticity of the material matrix are further supplemented.

In the embodiment of the present invention, the dynamic supramolecular cross-links formed by metal-ligand interactions and the supramolecular hydrogen bonding cross-links formed by supramolecular hydrogen bonding interactions may be in the same polymer network structure, or may be in different polymer network structures independently from each other, wherein independently from each other, the metal-ligand interactions and the supramolecular hydrogen bonding interactions are each independently in different non-crosslinked polymer chains or in different crosslinked polymer networks, and the formed crosslinked or non-crosslinked polymers are mutually blended or mutually interpenetrated. The dynamic polymer formed by mutually independent polymers is utilized, the dynamic properties of the components can be mutually matched and independently play a role, and therefore, better synergistic or orthogonal effect is embodied.

In an embodiment of the invention, the ligand group (represented by L) is selected from cyclopentadiene and a structural unit containing at least one coordinating atom (represented by a). A coordinating atom may form one or more coordination bonds to one or more metal centers (including, but not limited to, metal ions, metal centers of metal chelates, metal centers of metal organic compounds, metal centers of metal inorganic compounds, represented by M), and a metal center may also form one or more coordination bonds to one or more coordinating atoms. The number of coordination bonds formed by a ligand group and a metal center is called the number of teeth of the ligand group, in the embodiment of the present invention, in the same system, a metal center can form a metal-ligand action with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring by connecting through the metal center, so that the present invention can effectively provide dynamic metal-ligand actions with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:

wherein A is a coordinating atom, M is a metal center, and an A-M bond formed between each ligand group and the metal center is a tooth, wherein the A is connected by a single bond to indicate that the coordinating atoms belong to the same ligand group, and when two or more coordinating atoms are contained in one ligand group, A can be the same atom or different atoms, and is selected from the group consisting of but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. In some cases, a may be in the form of a negative ionThe formula (I) exists;

In embodiments of the invention, a metal center is capable of forming a metal-ligand interaction with at least two moieties of the ligand group (i.e., M-L) in order to form crosslinks based on the metal-ligand interaction ₂ Structure) or there may be multiple ligands forming a metal-ligand interaction with the same metal center, where two or more ligand groups may be the same or different. The coordination number of one metal center is limited, the more the coordinating atoms of the ligand groups are, the fewer the number of ligands that can be coordinated by one metal center is, and the lower the supramolecular cross-linking degree based on the metal-ligand effect is; however, since the more denticity each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, and thus, in the present invention, it is preferable that the number of ligand groups not exceed tridentate.

In embodiments of the invention, there may be only one ligand in a polymer chain or in a dynamic polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure, and a skeleton ligand, a side group ligand and a terminal group ligand can have the same core ligand structure, and the difference is that the connection points and/or positions of the core ligand structure connected to the polymer chain or the small molecule are different. Suitable ligand combinations can effectively produce dynamic polymers with specific properties, for example, to act synergistically and/or orthogonally to enhance the overall properties of the material. Suitable ligand groups (core ligand structures) may be exemplified by, but are not limited to, the following:

examples of monodentate ligand groups are as follows:

bidentate ligand groups are exemplified below:

tridentate ligand groups are exemplified below:

tetradentate ligand groups are exemplified below:

the polydentate ligands are exemplified by:

in embodiments of the present invention, when a non-covalently crosslinked polymer or small molecule compound is present in the dynamic polymer system, the core ligand structure may also serve as an end group at the end of the non-covalently crosslinked polymer or small molecule compound.

In embodiments of the present invention, the metal center M may be the metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.

The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).

More preferably, the metal is a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), or a metal of the actinide series (Th). Further preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th are selected to obtain stronger dynamic property.

In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:

other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

In the embodiment of the present invention, the metal inorganic compound is preferably an oxide or sulfide particle of the above metal, particularly a nanoparticle.

In embodiments of the present invention, the metal chelate complexes that may provide suitable metal centers are preferably those that have coordination site vacancies, or that have a portion of the ligands that may be replaced by the backbone ligands of the present invention.

In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can generate a suitable metal-ligand action with the metal center, but a metal-ligand action having a dynamic property at the use temperature of the material is preferable, and a metal-ligand action having a dynamic property at not higher than 25 ℃ is more preferable. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in the present invention, the supramolecular hydrogen bonding is generally a hydrogen bond linkage in the form of Z-H … Y through hydrogen mediated by a hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same or different element, and may be selected from atoms such as F, N, O, C, S, Cl, P, Br, I, more preferably F, N, O atom, and more preferably O, N atom.

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

The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:

the more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond action is weak, and the hydrogen bond can play a role in promoting the dynamic polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low and the dynamic properties of the hydrogen bond interaction are strong, which can provide dynamic properties together with the metal-ligand supramolecular interaction. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.

In an embodiment of the invention, the dynamic polymer contains said pendant hydrogen bonding groups comprising the following structural elements:

wherein X is selected from oxygen atom, sulfur atom, silicon atom and nitrogen atom, and Y is selected from oxygen atom and sulfur atom; a is R attached to the X atom ₂ The number of (2); when X is an oxygen atom or a sulfur atom, a is 0, R ₂ Is absent; when X is selected from nitrogen atoms, a ═ 1; when X is a silicon atom, a ═ 2; r ₁ 、R ₂ Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbyl groups having a molecular weight of no more than 1000 Da; j is a divalent linking group selected from the group consisting of single bonds, heteroatom linkers, divalent small molecule hydrocarbon groups having a molecular weight of no more than 1000 Da; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group having a molecular weight of not more than 1000 Da;

is represented by and polymerA backbone, a cross-linked network chain backbone, side chains (including multilevel structures thereof), or any other suitable group/atom linkage; wherein, J, R ₁ 、R ₂ And any two or more of Q may be linked to form a ring, wherein the ring includes, but is not limited to, an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, the ring-forming atoms of the ring structure are each independently a carbon atom, a nitrogen atom, or other heteroatoms, and the hydrogen atom on each ring-forming atom may or may not be substituted.

Examples of suitable pendant hydrogen bonding groups are (but the invention is not limited to):

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

Pendant hydrogen bonding groups have structural diversity including, but not limited to, the number of hydrogen bonding donors and acceptors, the size of the group, the length and rigidity of the linkage to the polymer chain; in addition, the number of pendant hydrogen bonding groups attached to the polymer chain is also widely adjustable. The side group hydrogen bond groups participate in forming the supermolecule hydrogen bond, so that the hydrogen bond effect with the strength, the dynamic property, the responsiveness and the crosslinking density adjustable in a large range can be obtained, meanwhile, the dynamic property of the hydrogen bond, the glass transition temperature of the crosslinked polymer and the like can be controlled through regulating and controlling the linkage with the polymer chain, and then various dynamic properties of the hybrid dynamic polymer are effectively regulated and controlled, and the polymer material with richer structure, more diversified performance and more hierarchical dynamic reversible effect is obtained. In order to ensure the dynamic property and the flexibility of the side group hydrogen bond group, the side group hydrogen bond group is of an independent structure and is not connected with any ligand group.

In the embodiment of the present invention, the hybrid supramolecular-acting dynamic polymer optionally contains suitable skeleton hydrogen bond groups (including non-crosslinked polymer backbone skeleton and supramolecular-acting crosslinked polymer network chain skeleton) and/or terminal hydrogen bond groups and other hydrogen bond groups participating in supramolecular hydrogen bonding, including intermolecular crosslinking, intramolecular ring formation, intermolecular polymerization and the like, so as to enrich the performance and tunability of the dynamic polymer.

In the present invention, the backbone hydrogen bonding group, in which at least a part of the atoms are part of the chain backbone, preferably contains the following structural elements:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein,

it represents a linkage to a backbone of a polymer backbone chain or a backbone of a cross-linked network chain.

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

in the present invention, the terminal hydrogen bonding groups may be any suitable hydrogen bonding groups.

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

In the present invention, the supramolecular hydrogen bonding may be generated during dynamic supramolecular cross-linking of dynamic polymers; or dynamic supermolecule crosslinking is carried out after the supermolecule hydrogen bond is generated in advance; it is also possible to generate supramolecular hydrogen bonding during subsequent formation of the dynamic polymer after the formation of dynamic supramolecular crosslinks, but the invention is not limited thereto.

According to the invention, the metal-ligand action, the dynamic property of the supermolecule hydrogen bond and the orthogonality and the cooperativity of the metal-ligand action and the supermolecule hydrogen bond are fully utilized to obtain the dynamic polymer with the characteristics of quick self-repairing and recycling, and the material can be endowed with excellent self-repairing property at normal temperature or other use temperatures; at the same time, the materials exhibit good processing properties and are easy to recycle and reuse, which is not possible with existing polymer systems. And by regulating and controlling parameters such as molecular structure, functional group number, molecular weight and the like of the compound serving as the raw material, the dynamic polymer with different structures, different apparent characteristics, adjustable performance and wide application can be prepared.

In embodiments of the present invention, the generation or introduction of ligand groups may employ any suitable reaction, including but not limited to the following types: reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl, electrophilic substitution of heterocycle, nucleophilic substitution of heterocycle, double bond free radical reaction, side chain reaction of heterocycle, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester with amino; preferably, the reaction of isocyanate with amino, hydroxyl and sulfhydryl, the azide-alkyne click reaction, the urea-amine reaction, the amidation reaction, the reaction of active ester with amino, and the sulfhydryl-double bond/alkyne click reaction; more preferably isocyanate with amino, hydroxyl, thiol reaction, thiol-double bond/alkyne click reaction, azide-alkyne click reaction.

In embodiments of the invention, the introduction of the metal centre may be carried out at any suitable time. There are at least three methods of introduction, either before the ligand groups are formed, after the polymerization/crosslinking of the metal-ligand interaction composition with the ligands has taken place, or after the polymerization/crosslinking has been completed. Preferably after the ligand groups are generated.

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

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

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

The monocyclic structure mentioned in the cyclic structure of the present invention means that the cyclic structure contains only one ring, for example:

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

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

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

when the structure referred to in the present invention has isomers, any isomer may be used without particular limitation, and includes positional isomers, conformational isomers, chiral isomers, cis-trans isomers and the like.

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

For a compound, a group or an atom, both substituted and hybridized, e.g. nitrophenyl for the hydrogen atom, again e.g. -CH ₂ -CH ₂ -CH ₂ -is replaced by-CH ₂ -S-CH(CH ₃ )-。

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

In the embodiment of the invention, the hybrid dynamic polymer and the composition thereof can be in the forms of solution, emulsion, paste, gum, common solid, elastomer, gel (including hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel and ionic liquid swollen gel), foam material and the like, wherein the content of soluble low molecular weight components in the common solid and the foam material is generally not higher than 10 wt%, and the content of low molecular weight components in the gel is generally not lower than 50 wt%. Solutions, emulsions, pastes, glues, ordinary solids, elastomers, gels, and foams are characterized and advantageous. The solution and the emulsion have good fluidity, can fully show shear thickening effect in fluid, and can prepare self-repairing coating by utilizing the coating property of the solution and the emulsion. Pastes are typically concentrated emulsions and gums are typically concentrated solutions or low glass transition temperature polymers that can exhibit good plasticity and fillability. The shape and volume of the common solid are fixed, the common solid has better mechanical strength and can not be restricted by a swelling agent. The elastomer has the general property of common solid, but has better elasticity and is softer, and the elastomer is favorable for buffering external acting force through deformation. Gels having good flexibility, exhibiting good variability and resilience, are preferred gels swollen by plasticizers, ionic liquids, oligomers and organic solvents having a boiling point higher than that of water. The foam material has the advantages of low density, lightness and high specific strength, can overcome the problems of brittleness of part of common solids and low mechanical strength of organogel, and has good elasticity and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

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

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

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

The physical foaming method is to realize the foaming of the polymer by using a physical principle in the preparation process of the dynamic polymer, and generally includes, but is not limited to, the following methods: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low boiling point liquid, i.e. pressing the low boiling point liquid into polymer or dissolving the liquid into polymer (particles) under certain pressure and temperature conditions, then heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out the solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. until the product is formed, then placing the product into water to make repeated treatment to dissolve out the soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into the material and then compounded to form closed cell foamed polymer; (5) a filling expandable particle method of mixing filling expandable particles and expanding the expandable particles during molding or mixing to actively foam the polymer material; among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer. The physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like. In addition, the preparation method can also adopt a freeze drying method.

The chemical foaming method is a method for foaming a dynamic polymer by generating gas along with a chemical reaction in a foaming process of the dynamic polymer, and includes, but is not limited to, the following two methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) to cause the polymer to expand and foam. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

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

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

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

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

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

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

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

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

The dynamic polymer material can be formed by adding some other polymers, auxiliary agents, fillers and swelling agents in the preparation process of the dynamic polymer, but the addition of the other polymers, the auxiliary agents, the fillers and the swelling agents is not necessary.

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

When the other polymer is selected from natural high molecular compounds, it can be selected from any one or several of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, polysaccharide, etc.

When the other polymer is selected from synthetic macromolecular compounds, it can be selected from any one or several of the following: polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinylidene chloride, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylate, polyacrylamide, polyacrylonitrile, polybenzimidazole, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinylpyrrolidone, epoxy resin, phenol-formaldehyde resin, urea-formaldehyde resin, unsaturated polyester, polyisoprene, polycistradiene, polydimethylsiloxane, poly (vinylidene chloride), poly (ethylene carbonate), poly (ethylene glycol), poly (ether sulfone), poly (arylene ether ketone), poly (ethylene-co-ether ketone), polyimide, polyacrylate, poly (phenylene oxide), poly (phenylene sulfide), poly (ethylene-co-phenylene sulfide), poly (ethylene-styrene), poly (ethylene-butylene-propylene), poly (ethylene-vinyl chloride), poly (ethylene-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-ethylene-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-propylene-co-ethylene-propylene-co-propylene-co-propylene-co-propylene-ethylene-propylene-co-propylene-, Polymethylvinylsiloxane, polymethylphenylsiloxane, polymethylvinylphenylsiloxane, polymethylvinyltrifluoropropylsiloxane, polyepichlorohydrin, and the like.

In the preparation process of the dynamic polymer material, some additive agents can be added, which can improve the material preparation process, improve the quality and yield of products, reduce the cost of the products or endow the products with certain specific application performance. The additive can be selected from any one or any several of the following additives: the synthesis auxiliary agent comprises a catalyst and an initiator; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; an auxiliary agent for improving mechanical properties, comprising a toughening agent; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer and a foaming agent; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents comprise nucleating agents, rheological agents, thickening agents, leveling agents and antibacterial agents.

The catalyst in the additive agent can accelerate the reaction rate of reactants in the reaction process by changing the reaction path and reducing the reaction activation energy. It includes, but is not limited to, any one or any of the following catalysts: catalyst for polyurethane synthesis: amine catalysts such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, 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, etc.; organometallic catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctanoate, lead isooctanoate, potassium oleate, zinc naphthenate, cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, etc.; ② a catalyst for polyolefin synthesis: such as Ziegler-Natta catalysts, pi-allylnickel, alkyllithium catalysts, metallocene catalysts, diethylaluminum monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, aluminum sesquiethylate chloride, vanadium oxychloride, triisobutylaluminum, nickel naphthenate, rare earth naphthenate, etc.; ③ CuAAC reaction catalyst: co-catalysis by monovalent copper compounds and amine ligands; the monovalent copper compound may be selected from Cu (I) salts such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; may also be selected from Cu (I) complexes, e.g. [ Cu (CH) ₃ CN) ₄ ]PF ₆ 、[Cu(CH ₃ CN) ₄ ]OTf、CuBr(PPh ₃ ) ₃ Etc.; the amine ligand may be selected from tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2,3-Triazol-4-yl) methyl]Amines (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, and the like; thiola-ene reaction catalyst: photocatalysts such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2-dimethoxy-2-phenylacetophenone and the like; nucleophilic reagent catalysts such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine, etc. The amount of the catalyst to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.

The initiator in the additive can cause the monomer molecules to be activated to generate free radicals during the polymerization reaction, so as to improve the reaction rate and promote the reaction to proceed, and the initiator includes but is not limited to any one or more of the following initiators: firstly, an initiator for radical polymerization: organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; ② initiator for living polymerization: such as 2,2,6, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine triad systems, etc.; (iii) initiator for ionic polymerization: such as butyl lithium, sodium/naphthalene systems, boron trifluoride/water systems, tin tetrachloride/alkyl halides systems, etc.; (iv) an initiator for coordination polymerization: such as titanium tetrachloride/triethylaluminum systems, zirconocene dichloride/methylaluminoxane systems, and the like; initiating agent for ring-opening polymerization: such as sodium methoxide, potassium methoxide, ethylenediamine, 1, 6-hexamethylene diisocyanate, stannous octoate, etc. Among them, the initiator is preferably lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, or potassium persulfate. The amount of the initiator to be used is not particularly limited, but is generally 0.1 to 1% by weight.

The antioxidant in the additive can delay the oxidation process of the polymer material, ensure that the material can be processed smoothly and prolong the service life of the polymer material, and comprises any one or more of the following antioxidants: hindered phenols such as 2, 6-di-t-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-t-butylphenol); sulfur-containing hindered phenols such as 4,4 '-thiobis- [ 3-methyl-6-t-butylphenol ], 2' -thiobis- [ 4-methyl-6-t-butylphenol ]; triazine-based hindered phenols such as 1,3, 5-bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-s-triazine; trimeric isocyanate hindered phenols such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate; amines, such as N, N ' -di (β -naphthyl) p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine; sulfur-containing species such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphites such as triphenyl phosphite, trisnonylphenyl phosphite, tris [2, 4-di-t-butylphenyl ] phosphite and the like, and among them, Tea Polyphenol (TP), Butylhydroxyanisole (BHA), dibutylhydroxytoluene (BHT), t-butylhydroquinone (TBHQ), tris [2, 4-di-t-butylphenyl ] phosphite (antioxidant 168), and pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) are preferable as the antioxidant. The amount of the antioxidant to be used is not particularly limited, but is usually 0.01 to 1% by weight.

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

The heat stabilizer in the additive can prevent the polymer material from generating chemical changes due to heating in the processing or using process, or delay the changes to achieve the purpose of prolonging the service life, and the heat stabilizer comprises but is not limited to any one or more of the following heat stabilizers: lead salts such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, isooctyl dimethyltin dimercaptoacetate, dimethyltin dimercaptolate, and combinations thereof; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; polyols, such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; composite heat stabilizers, such as coprecipitated metal soaps, liquid metal soap composite stabilizers, organotin composite stabilizers, and the like. Among them, barium stearate, calcium stearate, di-n-butyltin dilaurate and di (n) -butyltin maleate are preferable as the heat stabilizer, and the amount of the heat stabilizer used is not particularly limited, but is generally 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 bearing strength of the material, and the toughening agent comprises any one or more of the following toughening agents: the amount of the toughening agent used is not particularly limited, but is usually 5 to 10% by weight.

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

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

The plasticizer in the additive can increase the plasticity of the polymer material, reduce the hardness, modulus, softening temperature and brittle temperature of the polymer, and improve the elongation at break, flexibility and flexibility, and the package thereofIncluding but not limited to any one or any of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl glycolate butyl phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. epoxyglycerides, epoxyfatty acid monoesters, epoxytetrahydrophthalates, epoxysoya bean oil, epoxyhexyl (2-ethyl) stearate, epoxy2-ethylhexyl soyate, di (2-ethyl) hexyl 4, 5-epoxytetrahydrophthalate, methyl chrysene acetylricinoleate, glycols, e.g. C _5～9 Acid ethylene glycol ester, C _5～9 Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like. Among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP), and the amount of the plasticizer to be used is not particularly limited, but is usually 5 to 20% by weight.

The foaming agent in the additive can enable the polymer sample to be foamed into pores, so that a light, soft or rigid polymer material is obtained, and the foaming agent comprises any one or more of the following foaming agents: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, diethyl ether, methyl chloride, methylene chloride, ethylene dichloride, dichlorodifluoromethane, chlorotrifluoromethane; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylenetetramine, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azobisisobutyronitrile, 4' -oxybis-benzenesulfonylhydrazide, trihydrazinotriazine, p-toluenesulfonylaminourea, biphenyl-4, 4' -disulfonylazide; physical microsphere/particle blowing agents such as expandable microspheres manufactured by Acksonobel, et al; foaming promoters such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc. Among them, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylenetetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitrosoterephthalamide (foaming agent NTA), and physical microsphere foaming agents are preferable, and the amount of the foaming agent used is not particularly limited, but is usually 0.1 to 30 wt%.

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

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

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

The colorant in the additive can make the polymer product present the required color, and increase the surface color, which includes but not limited to any one or several of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. lithol rubine BK, lake Red C, perylene Red, Jia-base R Red, Phthalocyanine Red, permanent magenta HF3C, Plastic scarlet R and Clomomor Red BR, permanent orange HL, fast yellow G, Ciba Plastic yellow R, permanent yellow 3G, permanent yellow H ₂ G. Phthalocyanine blue B, phthalocyanine green, plastic purple RL and aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil soluble yellow, etc. The choice of the colorant is determined according to the color requirement of the sample, and the amount of the colorant is not particularly limited, and is generally 0.3-0.8 wt%.

The fluorescent whitening agent in the additive can enable the dyed material to obtain the fluorite-like flash luminescence effect, and the fluorescent whitening agent comprises any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like. Among them, the fluorescent brightener is preferably sodium distyrylbiphenyldisulfonate (fluorescent brightener CBS), 4-bis (5-methyl-2-benzoxazolyl) stilbene (fluorescent brightener KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent brightener OB-1), and the amount of the fluorescent brightener used is not particularly limited, and is generally 0.002 to 0.03 wt%.

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

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

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

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

The thickening agent in the additive can endow the polymer mixed solution with good thixotropy and proper consistency, thereby meeting the requirements of various aspects such as stability and application performance during production, storage and use, and the like, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, fatty alcohol-polyoxyethylene ether sulfates, alkyl dimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine; high molecular substances such as bentonite, artificial hectorite, micro-powder silicon dioxide, colloidal aluminum, plant polysaccharides, microorganism polysaccharides, animal proteins, alginic acids, polymethacrylate, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyether, and polyvinylmethylether urethane polymer. Among these, coconut oil diethanolamide is preferable as the thickener, and the amount of the thickener to be used is not particularly limited, but is usually 0.1 to 1.5% by weight.

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

The antibacterial agent in the additive can keep the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae, viruses and the like) below a necessary level within a certain period of time, and is generally divided into an inorganic antibacterial agent, an organic antibacterial agent and a natural antibacterial agent. Wherein, the inorganic antibacterial agent includes but not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, etc.; the organic antibacterial agent includes but is not limited to organic compounds such as vanillin, ethyl vanillin, acylaniline, imidazole, thiazole, isothiazolone derivative, quaternary ammonium salt, biguanidine and phenol; natural antimicrobial agents include, but are not limited to, chitin, mustard, castor oil, horseradish, and the like. The antibacterial agent is preferably silver, zinc, vanillin compounds, and ethyl vanillin compounds, and the amount of the antibacterial agent used is not particularly limited, but is generally 0.05 to 0.5 wt%.

The additive filler plays the following roles in the polymer material: reducing the shrinkage rate of a molded product, and improving the dimensional stability, surface smoothness, gloss or matt property and the like of the product; adjusting the viscosity of the material; the requirements of different properties are met, such as the improvement of the impact strength, the compression strength, the hardness, the rigidity and the modulus of the material, the improvement of the wear resistance, the improvement of the heat deformation temperature, the improvement of the electrical conductivity and the thermal conductivity and the like; improving the coloring effect of the pigment; endowing photostability and chemical resistance; sixthly, the capacity increasing effect is realized, the cost can be reduced, and the market competitiveness of the product is improved.

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

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

The metal filler which can be added includes simple metal, metal alloy, metal oxide, metal inorganic compound, metal organic compound, etc., which includes but is not limited to any one or any several of the following: powders, nanoparticles and fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; wherein the nanoparticles include, but are not limited to, gold nanoparticles, silver nanoparticles, palladium nanoparticles, cobalt nanoparticles, nickel nanoparticles, and magnetic nanoparticles (e.g., gamma-Fe) ₂ O ₃ 、CoFe ₂ O ₄ 、NiFe ₂ O ₄ 、MnFe ₂ O ₄ 、 Fe ₃ O ₄ 、FeN、Fe ₂ N、ε-Fe ₃ N、Fe ₁₆ N, etc.); also included are liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys; the metal organic compound comprises metal organic compound molecules or crystals which can generate heat under the action of ultraviolet rays, infrared rays or electromagnetism.

The organic filler which can be added comprises any one or any several of the following materials in a limiting way: fur, cotton linter, hemp, jute, flax, asbestos, shellac, lignin, protein, enzyme, hormone, raw lacquer, wood flour, shell flour, xylose, silk, rayon, vinylon, phenolic microbeads, resin microbeads, and the like.

The type of filler to be added is not limited, but depends on the desired material properties, and calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass beads, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, protein, and resin beads are preferred, and the amount of filler used is not particularly limited, but is generally 1 to 30 wt%.

In the preparation process of the dynamic polymer material, the auxiliary agents which can be added are preferably antioxidants, light stabilizers, heat stabilizers, toughening agents, plasticizers, foaming agents and flame retardants. Preferred fillers that can be added are calcium carbonate, barium sulfate, talc, carbon black, glass beads, graphene, glass fibers, carbon fibers.

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

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

The specific process for preparing hybrid dynamic polymers by solution stirring mixing is usually to mix the raw materials in dissolved or dispersed form in the respective solvents or in a common solvent in a reactor with stirring. Generally, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃ and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a suitable mold and placed at a temperature of 0-150 ℃, preferably 25-80 ℃ for 0-48h to obtain a polymer sample.

The solvent used in the above preparation method should be selected according to the actual conditions of the reactants, the products, the reaction process, etc., and includes, but is not limited to, any one of the following solvents or a mixture of any several solvents: deionized water, acetonitrile, acetone, butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, N-butyl acetate, trichloroethylene, mesitylene, dioxane, Tris buffer, citric acid buffer, acetic acid buffer, phosphoric acid buffer, etc.; deionized water, toluene, chloroform, dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, dimethylformamide, phosphoric acid buffer solution are preferred. In addition, the solvent can also be selected from oligomers, plasticizers, ionic liquids; the oligomer comprises but is not limited to polyethylene glycol oligomer, polyvinyl acetate oligomer, poly (n-butyl acrylate) oligomer, liquid paraffin and the like; the plasticizer can be selected from the plasticizer category in the additive auxiliary agents, and the description is omitted; the ionic liquid is generally composed of an organic cation and an inorganic anion, and the cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphine ion, a 1, 3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion and the like; the anion is typically a halide, tetrafluoroborate, hexafluorophosphate, or CF ₃ SO ₃ ^- 、(CF3SO ₂ ) ₂ N ^- 、C ₃ F ₇ COO ^- 、C ₄ F ₉ SO ₃ ^- 、CF ₃ COO ^- 、(CF ₃ SO ₂ ) ₃ C ^- 、 (C ₂ F ₅ SO ₂ ) ₃ C ^- 、(C ₂ F ₅ SO ₂ ) ₂ N ^- 、SbF ₆ ^- 、AsF ₆ ^- And the like. Wherein, when the dynamic polymer is prepared by using deionized water and is selected to be reserved, hydrogel can be obtained; when the dynamic polymer is prepared by using an organic solvent and selectively retained, organogel can be obtained; by using oligomersWhen preparing the dynamic polymer and selecting to reserve the dynamic polymer, the oligomer swelling gel can be obtained; when the plasticizer is used for preparing the dynamic polymer and is selected to be reserved, the plasticizer swelling gel can be obtained; when the ionic liquid is used for preparing the dynamic polymer and the dynamic polymer is selected to be reserved, the ionic liquid swelling gel can be obtained.

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

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

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

The hybrid supermolecule-action dynamic polymer has metal-ligand action and supermolecule hydrogen bonds formed by side hydrogen bond groups, so that the obtained dynamic polymer has excellent dynamic reversibility and good toughness, and through proper component selection and formula design, the material can be applied to the fields of military aerospace equipment, functional coatings, biomedicine, biomedical materials, energy sources, buildings, bionics, intelligent materials and the like, and has wide application prospects.

For example, the self-repairing property of the dynamic polymer is fully utilized, so that the adhesive with the self-repairing function can be prepared, and the adhesive is applied to the adhesion of various materials; the preparation method can also be used for preparing polymer plugging glue, sealing elements such as sealing plugs, sealing rings and the like which have good plasticity and can be recycled, or preparing wear-resistant and tear-resistant handle sleeves and the like; based on the metal-ligand action and the dynamic reversibility of side group hydrogen bonds, the scratch-resistant coating with the self-repairing function can be designed and prepared, so that the service life of the coating is prolonged, and long-acting corrosion protection on a matrix material is realized; through proper component selection and formula design, the polymer material with the self-repairing function can be prepared, so that the principle of organism injury healing can be simulated, the material can carry out self-healing on internal or external injuries, hidden dangers are eliminated, the service life of the material is prolonged, and the polymer material has great application potential in the fields of military industry, aerospace, electronics, bionics and the like.

For another example, the introduction of metal-ligand action and supramolecular hydrogen bonds enables the polymer material to show excellent toughness under the action of external force, so that polymer films, fibers or plates with excellent toughness can be obtained, and the polymer film, the fibers or the plates can be widely applied to the fields of military affairs, aerospace, sports, energy, buildings and the like; the material can also be used as a shape memory material, and when the external force is removed, the deformation of the material generated in the loading process can be recovered; the polymer can also be applied to oil extraction and fuel explosion prevention based on the dilatancy of the dynamic polymer, and the polymer material can also be applied to the manufacture of toys and fitness materials with the magic effect of viscous flow and high elastic conversion; based on the dynamic property of the dynamic polymer, the conductivity of the polymer composition is easy to generate sensitive response to external force under the condition of filling the conductive filler, and further the polymer composition can be used for preparing a force sensor.

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

Example 1

Adding 100mL of deionized water, 86g of methyl acrylate, 10.5g of 4-vinylpyridine and 20g of acrylate monomer containing a urea bond (isocyanate ethyl acrylate and n-propylamine are reacted in a solvent dichloromethane, the molar ratio of amino to isocyanate is kept to be 1:1 to prepare the acrylate monomer containing the urea bond), 1g of polyvinyl alcohol, 2g of fatty alcohol polyoxyethylene ether sulfate (AES) and 3g of azobisisobutyronitrile, stirring and mixing uniformly, pre-emulsifying the raw materials in an emulsifier, transferring the pre-emulsified liquid to a No. 2 reactor, adding 30mL of deionized water, stirring uniformly, heating to 80 ℃, reacting for 4 hours, cooling the product to below 40 ℃, and adjusting the pH of the product to 8-9 by using sodium bicarbonate to prepare a modified methyl acrylate emulsion; 31.5g of water, 2g of coconut oil diethanolamide, 1g of sodium dodecyl benzene sulfonate, 0.3g of mildew preventive Z, 1g of polyacrylate and 1g of defoaming agent are added into a No. 3 reactor, stirred for 10min, then 5g of titanium dioxide, 3g of lithopone, 1g of propylene glycol, 11g of light calcium carbonate, 1g of light stabilizer 770, 2g of pearl powder, 4g of talcum powder, 0.2g of sodium hexametaphosphate, 1.5g of methyl cellulose and 1g of silver trifluoromethanesulfonate are added, after high-speed dispersion is carried out for 30min, 50mL of modified methyl acrylate emulsion is added, the mixture is stirred uniformly, and the viscosity is adjusted by water, thus obtaining the dynamic polymer emulsion. The emulsion can be used as a coating, is coated on the surface of a protective guard, has an obvious light reflecting effect at night, can automatically heal when the coating is damaged and cracked, and prolongs the service life of the coating.

Example 2

Adding 21g of 4-vinylpyridine, 25g of olefin monomer containing hydrogen bond groups (cyanuric acid and 6-chloro-1-hexene are kept in a molar ratio of 4:1 and dissolved in anhydrous dimethyl sulfoxide) into a reactor No. 1, stirring and reacting for 15 hours at 80 ℃ under the catalysis of potassium carbonate to prepare the olefin monomer containing the hydrogen bond groups, 100g of styrene and 1g of potassium persulfate (KPS), uniformly stirring, heating to 80 ℃, reacting for 2 hours, adding proper amount of dimethyl sulfoxide (DMSO), adjusting the product to a solution with a certain concentration, then, 1g of [2,3,5, 6-tetrakis { (diethylamino) methyl } phenylene-1, 4-bis (platinum trifluoromethanesulfonate) ], 1g of fumed silica were added thereto, and dispersed by ultrasonic wave for 30 minutes, followed by stirring and mixing uniformly to obtain a dynamic polymer solution. The viscosity of the solution, as measured by a rotational viscometer, increases with increasing stirring speed. The material can be used as a thickening agent. .

Example 3

In a No. 1 reactor, under the protection of nitrogen, adding 4 '-carboxyl-2, 2':6', 2' -terpyridyl pyridine into aminated dimethyl siloxane (the average molecular weight is about 10000, and the m: n is about 3:2), adding a proper amount of condensing agent 1-Hydroxybenzotriazole (HOBT) and an activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to keep the molar ratio of urea to amino at 8:10, slowly heating to 160 ℃ under stirring, cooling to room temperature after keeping the temperature for about 1 hour, adding a proper amount of dichloromethane to dissolve the mixture, heating to 80 ℃ for refluxing, adding ethyl isocyanate with the same molar equivalent as the rest amino, reacting for 1 hour, and removing the solvent to obtain a product 1; 10g of product 1, 80g of dimethyl silicone oil, 5g of graphene, 3g of carbon fiber, 2g of gallium indium liquid metal, 1g of silane coupling agent, 1g of zinc chloride powder and a small amount of water are added into a No. 2 reactor, the mixture is uniformly stirred, dispersed for 30min by ultrasonic waves, placed into a vacuum oven at 80 ℃ and kept warm for 4h, and cooled to obtain the dynamic polymer paste. The paste has strong heat conduction and electric conduction performance, and can be prepared into self-repairing heat conduction and electric conduction coating paste for use.

Example 4

Adding liquid polyvinyl alcohol and a small amount of triethylamine into a No. 1 reactor while stirring, then adding 2, 6-dichloro-4-pyridyl isocyanate and a small amount of [2,3,5, 6-tetra { (dimethylamino) methyl } -phenylene-1, 4-bis (palladium trifluoromethanesulfonate) ] to keep the molar ratio of isocyanate groups to hydroxyl groups at 1:3, adding a small amount of catalyst triethylamine, heating to 80 ℃, stirring for 2h, continuously adding a proper amount of isopropyl isocyanate, completely reacting the residual hydroxyl groups, discharging when the reaction is hot after 2h, and placing the product in a brown container for keeping out of the sun to prepare the dynamic polymer jelly. The jelly has strong adhesive capacity and good self-repairing performance, and can be used as glass sealant.

Example 5

In a No. 1 reactor, dissolving acrylamide and ethyl isocyanate in toluene according to a molar ratio of 1:1, and taking triethylamine as a catalyst to prepare a product 1 containing a urea bond; adding acrylamide, 3-allyl-5-methyl-1H-pyrrolo [2,3-b ] pyridine and the product 1 into a No. 2 reactor, controlling the molar ratio of the acrylamide to the 3-allyl-5-methyl-1H-pyrrolo [2,3-b ] pyridine to be 5:4:1, then adding a certain amount of deionized water, a copper chloride solution and a small amount of potassium persulfate, stirring and mixing uniformly, placing under a 300W ultraviolet lamp for irradiating for 30min, taking out and cooling to obtain the dynamic polymer hydrogel. The hydrogel has certain toughness and self-repairing capability, and can be made into gel toy pellets which swell in water after being added with pigments.

Example 6

Dissolving 1 molar equivalent of polyacrylonitrile (the average molecular weight is about 10000), 20 molar equivalents of 3- (azidomethyl) pyridine, 20 molar equivalents of 2, 5-dehydration-1-azido-1-deoxy-D-glucitol, 100 molar equivalents of zinc chloride and a small amount of gas phase silicon dioxide and nano ferroferric oxide in dimethylformamide, performing ultrasonic treatment at room temperature for 5min to fully mix the components uniformly, heating to 125 ℃, and stirring for reaction to obtain a modified polyacrylonitrile product 1; reacting the modified polyacrylonitrile product 1 with ethyl isocyanate with the sum of hydroxyl groups of the equivalent molar weight in dimethyl sulfoxide to obtain a modified polyacrylonitrile product 2 with carbamate-containing side groups; adding zinc trifluoromethanesulfonate solution into a proper amount of the modified polyacrylonitrile product 2, uniformly stirring, and then swelling the mixture in dioctyl phthalate for 6 hours to prepare the dynamic polymer plasticizer swelling gel. The plasticizer swelling gel can also show certain shape memory characteristics under the action of an external magnetic field, and can be prepared into a shape memory material for use.

Example 7

In reactor No. 1, polyacrylic resin (average molecular weight about 3000), a small amount of condensing agent 1-Hydroxybenzotriazole (HOBT) and a small amount of activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) are added, dissolved in N, N-dimethylformamide and stirred uniformly, and then 4-amino-2, 6-diacetylpyridine (prepared by reacting 4-chloro-2, 6-diacetylpyridine with a hydrazine hydrate solution of phthalimide potassium) is added, wherein the molar ratio of amino groups to carboxyl groups is controlled to be 1: and 2, controlling the room temperature to continue stirring and reacting for 12 hours, adding N-acetyl ethylenediamine, adding a ferric chloride solution after the residual carboxyl is completely reacted, uniformly stirring, removing N, N-dimethylformamide, adding a certain amount of mixed solution of Span-80 and Tween-80, swelling for 24 hours, and removing the redundant solution to obtain the dynamic polymer organogel. The gel has certain self-repairing performance and toughness, can be prepared into self-adhesive epidermal drug delivery gel for use, is easy to adhere and is not easy to damage.

Example 8

Dissolving 2-aminoethyl acrylate and 4-biphenylyl formyl chloride with equal molar equivalent in dichloromethane in a No. 1 reactor, and preparing an acrylate monomer containing amido bond under the catalysis of triethylamine; adding 3-isocyanato-1-propylene and a small amount of triethylamine into a No. 2 dry reactor, heating to 80 ℃ while stirring, maintaining the temperature, adding 5- (aminomethyl) -2- (1-pyrazolyl) pyridine while stirring, controlling the molar ratio of isocyanato to amino to be 1:1, reacting for 2 hours, adding acrylic ester monomer containing amido bond and azodiisobutyronitrile in the same molar amount as 3-isocyanato-1-propylene, stirring and polymerizing for 2 hr, swelling the product in 1-ethyl-3-methylimidazolium tetrafluoroborate and dimethylformamide solvent with equal mass, adding 2 wt% of nickel chloride and 10 wt% of graphene, uniformly stirring, performing ultrasonic treatment for 20min, swelling for 24h, and removing the solvent to obtain the dynamic polymer ionic liquid swelling gel. After the surface of the sample is pressed by fingers, the sample can show good elasticity and can be stretched and expanded in a large range. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X 2.0mm, and subjected to a tensile test using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 0.73. + -. 0.15MPa and an elongation at break of 424. + -. 45%. The polymer sample in the embodiment has good self-repairing performance, after the polymer sample is cut off by a knife, pressure is slightly applied to the section for attaching, and the section can be bonded again after 90 min. The dynamic polymer sample in this embodiment can be used as a supercapacitor due to the high conductivity of graphene.

Example 9

Adding methacrylic acid, 2, 6-dimethoxypyridine-4-amine, a small amount of condensing agent 1-Hydroxybenzotriazole (HOBT) and a small amount of activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into a No. 1 reactor, controlling the molar ratio of carboxyl to amino to be 1:1, mixing and dissolving in tetrahydrofuran, stirring and reacting for 12 hours at room temperature, and removing the solvent after the reaction is finished to obtain a product 1; mixing the product 1, (butyl) -N-propyl-2-enamide and methyl acrylate, controlling the molar ratio of the product 1 to the product to be 2:2:5, and adding 1 wt% of Zn ₄ O(BTB) ₂ (MOF-177), adding a small amount of a photoinitiator ketoglutaric acid and a thermal initiator KPS, uniformly mixing the mixed solution with sufficient alkyl-terminated polyethylene glycol oligomer, irradiating for 30min under 300W ultraviolet and the like, taking out and cooling to obtain the dynamic polymer oligomer swelling gel. The polymer is made into dumbbell-shaped sample bars with the size of 80.0 multiplied by 10.0 multiplied by 2.0mm, a tensile testing machine is used for carrying out tensile test, the tensile rate is 50mm/min, the tensile strength of the sample is 1.33 plus or minus 0.25MPa, the elongation at break is 543 plus or minus 64 percent, the polymers after being broken are contacted together, and the adhesion is carried out again after 60 min. The dynamic polymer has good toughness and self-repairing capability, and can be prepared into a self-repairing sealing material with good sealing effect. Under the action of tensile force, the tensile strength and the elongation at break of the dynamic polymer are improved to a certain extent by the synergistic effect between the hydrogen bond and the metal-ligand action, and the product can be prepared into a tough adhesive for use. When the gel is in a polar solvent, the hydrogen bond effect of the gel is weakened, the mechanical property of the gel is reduced, and the metal-ligand effect and the hydrogen bond present orthogonal mechanical effect in a polar solvent environment.

Example 10

Dissolving polyacrylonitrile (average molecular weight is about 10000)1 molar equivalent, 3- (azidomethyl) pyridine 10 molar equivalent, 2, 5-dehydration-1-azido-1-deoxy-D-glucitol 10 molar equivalent, 2-azido ethylamine 10 molar equivalent and zinc chloride 100 molar equivalent in dimethylformamide, performing ultrasonic treatment at room temperature for 5min to fully and uniformly mix the components, heating to 125 ℃, and stirring for reaction to obtain a modified polyacrylonitrile product 1; reacting the modified polyacrylonitrile product 1 with isopropyl isocyanate with the sum of hydroxyl and amino in the same molar equivalent in dimethyl sulfoxide to obtain a modified polyacrylonitrile product 2 with side groups containing carbamate and urea bonds; fully mixing 100 parts by mass of modified polyacrylonitrile product 2,2 parts by mass of copper sulfate pentahydrate, 6 parts by mass of azodicarbonamide, 5 parts by mass of foamable particles and 1 part by mass of tribasic lead sulfate, placing the mixture in a proper mould, carrying out mould pressing foaming at 170 ℃ and 3.5Mpa, continuously curing for 2 hours at 100 ℃, and cooling to obtain the dynamic polymer foam material. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 70 percent compression strength of the sample is measured to be 0.74 +/-0.12 MPa. The obtained polymer foam material is light and soft, can be repaired again after being torn, and can be used as a heat-insulating material.

Example 11

Under the anhydrous and oxygen-free conditions, dissolving an ethylene-vinyl acetate-vinyl alcohol random polymer (the average polymerization degree is about 2000, and the molar ratio of an ethylene monomer to a vinyl acetate monomer to a vinyl alcohol monomer is about 1:1:2) in dichloromethane, adding 0.5-time molar equivalent of hydroxyl ethyl isocyanate and 0.5-time molar equivalent of 6-isocyanate quinoline, and reacting under the catalysis of triethylamine to obtain the ethylene-vinyl acetate random polymer with a pendant carbamate group and a ligand. The dynamic polymer foam material is prepared by the steps of fully mixing 100 parts by mass of the polymer, 1 part by mass of dicumyl peroxide, 8 parts by mass of N, N '-dimethyl-N, N' -dinitrosoterephthalamide (foaming agent NTA), 1 part by mass of tribasic lead sulfate, 3 parts by mass of foaming microspheres, 1 part by mass of conductive carbon black and 1 part by mass of carbon nano tubes, placing the mixture into a proper mold, performing foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 90-105 ℃, the molding time is 10-15min, and the pressure is 10MPa, after foaming molding, placing the mixture into an oven at 80 ℃ for continuous curing for 6h, and then cooling and taking out a sample. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 2.21 +/-0.53 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, is easy to form, can be automatically repaired after being damaged and cracked, and can be used as a stress sensing material when the resistivity of the polymer foam material is measured to be changed along with the stress applied to the polymer foam material.

Example 12

Adding 1 molar equivalent of 2,2 '-bipyridine-5, 5' -dinitrile, 2 molar equivalent of 2-azido ethylamine and 50 molar equivalents of zinc chloride into a reactor No. 1, dissolving in dimethylformamide, mixing at room temperature, heating to 125 ℃, stirring for reaction for 6 hours, cooling to 80 ℃, adding 2 molar equivalents of 3-isocyanate-1-propylene and 0.01 molar equivalent of triethylamine, and continuing to react for 2 hours to obtain a product 1 for later use; adding 1.5 molar equivalent of the product 1, 0.05 molar equivalent of the antioxidant 168 and 1 molar equivalent of 1, 3-propanedithiol-2-ol into a No. 2 reactor, uniformly mixing, then placing the mixture under a 300W ultraviolet lamp for irradiating for 30min, and fully reacting the prepared product with 1 molar equivalent of isopropyl isocyanate under the catalysis of triethylamine to prepare a product 2; mixing 100 parts by mass of a product 2,5 parts by mass of an AC foaming agent, 10 parts by mass of glass beads and 1 part by mass of cerium trifluoromethanesulfonate, then placing the mixture in an internal mixer for mixing for 30min, taking out a sizing material, placing the sizing material in a proper mold, and carrying out foam molding by using a flat vulcanizing machine, wherein the mold pressing temperature is 100-130 ℃, the mold pressing time is 10-15min, the pressure is 10MPa, after molding, placing the foam in a 60 ℃ drying oven for continuous curing for 4h, and cooling to obtain the dynamic polymer foam material which has good rigidity and strength. The sample was prepared into a block sample of 20.0X 20.0mm size, and a compression performance test was carried out by a universal tester at a compression rate of 2mm/min to obtain a 10% compressive strength of the sample of 3.42. + -. 0.63 MPa. The obtained polymer foam material has light specific gravity and high strength, can be automatically repaired after being damaged and cracked, and can be used as a light shell material.

Example 13

Fully reacting 1 molar equivalent of acrylic acid with 1 molar equivalent of 7-aminoimidazo [1,2-a ] pyridine to prepare a product 1; fully reacting 1 molar equivalent of acrylamide with 1 molar equivalent of ethyl isocyanate to obtain a product 2; 100 parts by mass of propylene, 10 parts by mass of product 1, 30 parts by mass of product 2, 0.5 part by mass of silver fluoroborate and 1 part by mass of nano calcium carbonate are uniformly mixed, and polymerization reaction is carried out under the combined action of titanium trichloride and triethyl aluminum, so as to prepare the random polypropylene-based dynamic polymer elastomer. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X 2.0mm, and subjected to a tensile test using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 13.23. + -. 3.14MPa and an elongation at break of 142.34. + -. 43.54%. The product can be prepared into a tough elastomer material for use.

Example 14

Adding 1 molar equivalent of polyether ketone powder with a side group containing carboxyl, 0.01 molar equivalent of condensing agent 1-Hydroxybenzotriazole (HOBT) and 0.012 molar equivalent of activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into a No. 1 reactor, dissolving in enough toluene, stirring until the materials are dissolved and mixed uniformly, adding 0.5 time of N, N-dimethylpyridine-2, 6-diimine with molar equivalent of carboxyl, continuously stirring at room temperature for reaction for 12 hours, then adding 0.5 time of ethyl isocyanate with molar equivalent of carboxyl and 0.01 molar equivalent of triethylamine, heating to 80 ℃, continuously reacting for 4 hours, removing the solvent, and preparing a product 1 for later use; and mixing 30 parts by mass of the product 1 with 100 parts by mass of polyether ketone, adding 0.5 part by mass of nano ferroferric oxide and 1 part by mass of nano talcum powder, and carrying out extrusion, granulation and injection molding to obtain the dynamic polymer common solid. A dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by 2.0mm is used for tensile test by a tensile testing machine, the tensile rate is 10mm/min, the tensile strength of the sample is 36.34 plus or minus 4.48MPa, the elongation at break is 62.27 plus or minus 14.25 percent, the sample can be made into an electronic device shell by utilizing the surface hardness and the high strength, and the surface scratch can be automatically repaired and healed.

Example 15

Adding 1 molar equivalent of polyacrylic resin with the relative molecular weight of 5000, enough solvent N, N-dimethylformamide, 0.01 molar equivalent of condensing agent 1-Hydroxybenzotriazole (HOBT) and 0.012 molar equivalent of activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into a No. 1 reactor, stirring and mixing uniformly, adding 0.5 molar equivalent of 4-amino-2, 6-diacetylpyridine (prepared by reacting 4-chloro-2, 6-diacetylpyridine with hydrazine hydrate solution of phthalimide potassium) and 0.3 molar equivalent of 5- (2-aminoethyl) pyrimidine-2, 4- (1H,3H) -diketone, reacting for 12H, and removing the solvent to prepare a product 1; fully mixing 100 parts by mass of a polymethyl acrylate oligomer, 50 parts by mass of a product 1,2 parts by mass of a nickelocene polymer, 0.5 part by mass of pyridine and 1 part by mass of zinc trifluoromethanesulfonate, dissolving the mixture in a proper amount of dimethyl sulfoxide, adding 0.3 part by mass of nano silicon dioxide, ultrasonically dispersing the nano silicon dioxide by using ultrasonic waves, and adjusting a solvent to a certain concentration to prepare the dynamic polymer jelly. The viscosity of the product can be changed along with the change of the shearing force, when the shearing force is large, the viscosity of the product is increased, the phenomenon of shear thickening is caused, and the product can be made into self-repairing bonding glue for use.

Example 16

Adding 1 molar equivalent of DL-1, 4-dithiothreitol, 0.8 molar equivalent of 3-allyl-5-methyl-1H-pyrrolo [2,3-b ] pyridine, 1.5 molar equivalent of product 1 (formed by reaction of N-butyl urea and allyl isocyanate with equal molar equivalent under catalysis of triethylamine) and 0.1 molar equivalent of antioxidant 1010 into a No. 1 reactor, uniformly mixing, placing under a 300W ultraviolet lamp for irradiating for 30min, taking out and cooling to obtain a product 2 for later use; the preparation method comprises the following steps of uniformly mixing 10 parts by mass of a product 2, 1 part by mass of diethyltoluenediamine (DETDA), 0.5 part by mass of dibutyltin dilaurate (DY-12), 2 parts by mass of dichloromethane, 12 parts by mass of HDI, 0.5 part by mass of palladium (II) propionate and 2 parts by mass of water, putting the mixture into a proper mold, uniformly mixing the mixture by using a special stirrer, heating the mixture to 80 ℃ to react and foam the mixture, putting the foam into a 60 ℃ oven to continuously cure the foam for 6 hours after the foaming is finished, thus obtaining the dynamic polymer foam material, preparing the dynamic polymer foam material into a block sample with the size of 20.0 x 20.0mm, and carrying out compression performance test by using a universal tester, wherein the compression rate is 2mm/min, and the 70% compression strength of the sample is measured to be 0.74 +/-0.12 MPa. The obtained polymer foam material has light specific gravity and is very soft, can automatically restore after being damaged and cracked, and can be used as the filling material in the cloth doll toy.

Example 17

Under the anhydrous and anaerobic condition, allyl mercaptan and equal molar equivalent of ethyl isocyanate react in dichloromethane under the catalysis of triethylamine to obtain an allyl monomer product 1 containing thiocarbamate groups. Adding 1 molar equivalent of methyl eugenol, 0.5 molar equivalent of product 1, 0.3 molar equivalent of 4, 6-dichloro-5- (2-propylene-1-yl) pyrimidine and 0.2 molar equivalent of AIBN into a reactor 1, stirring and mixing uniformly, heating to 90 ℃, reacting for 4 hours, and cooling to obtain a product 2; 100 parts by mass of a product 2, 7 parts by mass of an AC foaming agent, 5 parts by mass of foamed microspheres, 0.1 part by mass of a metal organic molecular cage (MOC-16), 8 parts by mass of calcium carbonate, 0.5 part by mass of stearic acid, 0.1 part by mass of an antioxidant 168 and 0.5 part by mass of di-n-butyltin dilaurate are uniformly mixed and added into a small internal mixer for internal mixing and blending, wherein the blending temperature is 100 ℃, the blending time is 30min, after the mixing is finished, a sample is taken out, is put into a double-roller machine to be pressed into a sheet, is placed in a vacuum oven at the temperature of 80 ℃ for 6h for further reaction and drying, is cooled to room temperature and is placed for 30 min. Taking out the mixing sample piece, placing the mixing sample piece in a proper mould, and carrying out foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 130-140 ℃, the molding time is 10-15min, and the pressure is 10MPa, so that the dynamic polymer foam material with good softness and elasticity is finally obtained. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 2.35 +/-0.21 MPa. After the polymer material is cut off, the polymer material can be reshaped by applying pressure on the section of the polymer material after being cut off, and the polymer material can be repeatedly used by utilizing the self-repairing property of the polymer material. In the present embodiment, it can be used for manufacturing an automotive interior material.

Example 18

Carrying out condensation reaction on 1 molar equivalent of 2, 6-diaminopyridine and 1.2 molar equivalents of 1, 3-phthalic acid under the action of a condensing agent 1-Hydroxybenzotriazole (HOBT) and an activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to prepare a product 1 with carboxyl groups at two ends; uniformly mixing 50 parts by mass of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl formate, 10 parts by mass of product 1 and 3 parts by mass of lauryl trimethyl ammonium chloride, heating to 100 ℃, reacting for 12 hours, adding 5 parts by mass of ethyl isocyanate and 0.1 part by mass of triethylamine, continuing to react for 2 hours, and cooling to obtain product 2; uniformly mixing 50 parts by mass of a product 2,5 parts by mass of diethyl azodicarboxylate, 3 parts by mass of glass microspheres, 2 parts by mass of glass fibers, 4 parts by mass of calcium carbonate, 1 part by mass of stearic acid, 0.1 part by mass of antioxidant 168 and 0.5 part by mass of di-n-butyltin dilaurate, putting the mixture into a proper mold, and carrying out foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 110 plus 120 ℃, the molding time is 10-15min and the pressure is 10MPa, placing the foam into a 60 ℃ oven for continuous curing for 4h after molding, and cooling to obtain the dynamic polymer foam material. The sample is made into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by a universal testing machine, the compression rate is 2mm/min, and the 10% compression strength of the sample is 3.32 plus or minus 0.41 MPa. The obtained polymer foam material has light specific gravity and high strength, can be automatically repaired after cracking, and can be used as a self-repairing foam board.

Example 19

Dissolving allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidinone in toluene according to the molar ratio of 1:1, taking potassium carbonate as a catalyst and tetrabutylammonium bromide as a phase transfer agent to obtain a product 1 with one end being allyl and the other end being oxazolidinone; heating 3-isocyanato-1-propylene and 4-hydroxypyridazine with equal molar equivalent to 80 ℃ to react under the catalysis of triethylamine, thus obtaining a product 2 with one end being allyl and the other end being ligand; 1 molar equivalent of hydrogen-containing silicone oil (average molecular weight about 20000, molar ratio of the repeating unit containing silicon and the repeating unit containing no silicon and hydrogen is about 1:2), 15 molar equivalents of product 1, 20 molar equivalents of product 2, and quaternary ammonium base 7% of total mass of silicone oil were thoroughly mixed and placed in a mold. And heating to 170 ℃, preserving the heat for 10 minutes, cooling and demoulding to obtain the silicone rubber elastomer. The resulting specimen was used as a dumbbell specimen having a size of 80.0X 10.0X 2.0mm, and a tensile test was carried out using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 0.54. + -. 0.11MPa and an elongation at break of 542.34. + -. 53.23%. The composite material can be made into a self-repairing coating or a self-repairing elastomer, and is applied to sealing and waterproofing of components of electronic products.

Example 20

Carrying out condensation reaction on 1 molar equivalent of 3- (2-oxo-1-azepanyl) propionic acid and 1 molar equivalent of 4 '-amino-2, 2':6', 2' -terpyridine under the action of a condensing agent 1-Hydroxybenzotriazole (HOBT) and an activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to prepare a product 1; carrying out condensation reaction on 1 molar equivalent of 3- (2-oxo-1-azepanyl) propionic acid and 1 molar equivalent of ethyl urea under the action of a condensing agent 1-Hydroxybenzotriazole (HOBT) and an activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to prepare a product 2; adding 200 g of caprolactam, 40g of the product 1 and 50g of the product 2 into a No. 3 reactor, heating to 175 ℃, stirring, mixing, vacuumizing for 20min, adding 1.2g of sodium hydroxide, continuously vacuumizing for 20min, then adding 2g of nano ferroferric oxide and 10g of glass fiber, dispersing by ultrasonic waves, adding 3g of toluene diisocyanate, pouring the mixture into a mold when the reactant becomes viscous, preserving the heat for 40min at 180 ℃, and cooling to obtain the ordinary dynamic polymer solid. The polymer is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by 2.0mm, a tensile test is carried out by a tensile testing machine, the tensile rate is 10mm/min, the tensile strength of the sample is 44.37 +/-7.75 MPa, the elongation at break is 84.34 +/-13.34 percent, and the prepared polymer sample has larger surface hardness and strength. The product can be made into a self-repairing material and can automatically heal when microcracks exist.

Example 21

Adding 57g of (2, 6-bis (dimethylamino) pyridin-4-yl) methacrylate, 18g of 3-buten-1-ol and 5g of azobisisobutyronitrile into a No. 1 reactor, uniformly stirring, heating to 90 ℃, continuing to react for 4 hours, adding 17g of ethyl isocyanate and 0.3g of triethylamine, continuing to react for 1 hour, and cooling to obtain a product 1; fully mixing 100 parts by mass of product 1,1 part by mass of zinc chloride, 0.5 part by mass of ruthenium pyridine, 1 part by mass of ferroferric oxide, 5.5 parts by mass of azodicarbonamide and 1 part by mass of calcium stearate, placing the mixture in a mold, plasticizing and foaming at 140 ℃ under the pressure of 5MPa, curing at 100 ℃ for 60 minutes, cooling and demolding to obtain the dynamic polymer foam material. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 70 percent compression strength of the sample is measured to be 1.15 +/-0.23 MPa. The obtained polymer foam material is light and soft, can be automatically repaired after cracking, has response performance to magnetism, and can be made into a shape memory material for use.

Example 22

Adding 100mL of toluene, 30g of polyvinyl alcohol (molecular weight 2000) and 1g of triethylamine into a No. 1 reactor, stirring for dissolving, heating to 80 ℃, adding 6.2g of 2, 6-dichloro-4-isocyanuric acid pyrimidine and 6.8g of ethyl isocyanate, continuously stirring for reacting for 1 hour, and removing the solvent to obtain a product 1; adding 35g of product 1, 1g of dibutyltin dilaurate, 1g of triethylamine, 1g of carbon fiber, 5g of conductive carbon black, 1g of glycerol, 1g of organic silicon oil, 3mL of 0.2mol/L ferric chloride solution and 3g of azodicarbonamide into a No. 3 reactor, uniformly mixing, putting into a proper mold, performing foam molding by using a flat vulcanizing machine, wherein the mold pressing temperature is 140-150 ℃, the mold pressing time is 10-15min, and the pressure is 10MPa, curing the molded product in an oven at 80 ℃ for 12h, taking out and cooling to obtain the dynamic polymer foam material. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 70 percent compression strength of the sample is measured to be 0.57 +/-0.12 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, has different resistivity under different stresses, can be automatically repaired after cracking, and can be used as a soft and sensitive stress sensor.

Example 23

Adding 40g of 2-propylene tetrazolyl-1, 10-phenanthroline (prepared by click reaction of 2-cyano-1, 10-phenanthroline and 3-azido-1-propylene under catalysis of triethylamine hydrochloride and toluene), 80g of methyl acrylate, 100mL of deionized water and 1g of potassium persulfate into a reactor No. 1, stirring and mixing uniformly, heating to 80 ℃, reacting for 4 hours, removing the solvent and drying a product 1 for later use; dissolving 2-aminoethyl acrylate and 4-biphenyl formyl chloride with equal molar equivalent in dichloromethane, and obtaining an acrylate monomer product 2 containing amido bond under the catalysis of triethylamine for later use; adding 50 parts by mass of methyl acrylate, 20 parts by mass of the product 1, 20 parts by mass of the product 2,3 parts by mass of initiator AIBN and 1 part by mass of hydrogen peroxide into a No. 2 reactor, stirring and mixing, heating to 80 ℃, and reacting for 4 hours to obtain a product 3. Adding 10 parts by mass of product 3, 2 parts by mass of N, N '-dimethyl-N, N' -dinitrosoterephthalamide (foaming agent NTA), 1 part by mass of glass fiber, 1 part by mass of glass beads, 0.2 part by mass of Ce-TBMN metal organic cage compound, 1.5 part by mass of stearic acid and 0.5 part by mass of di-N-butyltin dilaurate into a No. 3 reactor, uniformly mixing, adding into a small internal mixer for internal mixing and blending, wherein the blending temperature is 100 ℃, the blending time is 30min, taking out a sample after the blending is finished, putting the sample into a double-roller machine for pressing to form a sheet, cooling to room temperature, and standing for 30 min. Taking out the mixing sample sheet, placing the mixing sample sheet in a proper mould, and carrying out foaming molding by using a flat vulcanizing machine, wherein the mould pressing temperature is 90-105 ℃, the mould pressing time is 10-15min, and the pressure is 10MPa, so that the dynamic polymer foam material is finally obtained, and has good rigidity and rebound resilience. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 2.31 +/-0.45 MPa. The obtained polymer foam material has light specific gravity and easy molding, can automatically repair after being damaged, and can be used as a heat-insulating material.

Example 24

Adding 20 parts by mass of polyether ketone powder with a carboxyl-containing side group, 100 parts by mass of toluene, 0.3 part by mass of condensing agent 1-Hydroxybenzotriazole (HOBT) and 0.5 part by mass of activating agent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) into a No. 1 reactor, stirring until the materials are dissolved and mixed uniformly, adding 5 parts by mass of N, N-dimethylpyridine-2, 6-diimine and 5 parts by mass of dicyclohexylurea, and continuously stirring and reacting at room temperature for 12 hours to obtain a product 1 for later use; 10 parts by mass of the product 1,1 part by mass of glass fiber, 1 part by mass of nano calcium carbonate, 2 parts by mass of a foaming agent (a mixture of citric acid, sodium bicarbonate and sodium carbonate) and 0.5 part by mass of copper sulfate are extruded and foamed by utilizing a professional extrusion foaming agent, wherein the extrusion temperature is 350 ℃, and the dynamic polymer foam material is prepared and has good rigidity and strength. The sample is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a compression performance test is carried out by using a universal tester, the compression rate is 2mm/min, and the 10% compression strength of the sample is measured to be 15.23 +/-1.32 MPa. The obtained polymer foam material has light specific gravity and is easy to form, can be automatically repaired after being damaged, and can be used as a buoyancy material to be applied to a buoy of an amphibious tank.

Example 25

Mixing a certain amount of 5-cyclooctene-1, 2-diol, 2-imidazolidinone-4-carboxylic acid and 2- (pyrimidine-2-yl) pyrimidine-5-formic acid, controlling the molar ratio of the three to be about 1:1:1, and preparing a product 1 containing a hydrogen bond group and a ligand group simultaneously by using dicycloethyl carbodiimide and 4-dimethylaminopyridine as catalysts and dichloromethane as a solvent; mixing a certain amount of the product 1 and cyclooctene, controlling the molar mass ratio of the two to be about 1:2, taking Grubbs second-generation catalyst as a catalyst, taking dichloromethane as a solvent, adding a proper amount of platinum trifluoromethanesulfonate, uniformly coating the polymer solution which is completely reacted on a polyvinyl chloride plate, and preparing the dynamic polymer film after the solvent is completely volatilized. The specimen was cut into a dumbbell-shaped specimen having a size of 80.0X 10.0X (0.08. + -. 0.02) mm, and subjected to a tensile test using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 3.13. + -. 0.34MPa and an elongation at break of 523. + -. 45%. The obtained polymer film is soft in texture and high in toughness, a sample is recovered after being snapped, and can be re-filmed and reused after being placed in a mold and being attached for 1-3 hours, so that the polymer film can be made into a soft material scratch-resistant film for use.

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

Claims

1. A hybrid supramolecular-acting dynamic polymer comprising a metal-ligand interaction and supramolecular hydrogen bonding interactions formed by participation of pendant hydrogen bonding groups; at least one of the polymer chain skeleton, the side group and the end group of the dynamic polymer contains a ligand group; at least two atoms of the ligand groups on the polymer chain backbone participate directly in the construction of the polymer chain backbone; all atoms of the ligand groups on the pendant groups are on pendant groups; all atoms of the ligand groups on the terminal groups are on the terminal groups; wherein said metal-ligand interaction is selected from the following structures:

wherein A is a coordinating atom, M is a metal center, and each ligand group is bonded to the metal centerOne a-M key is formed as a tooth,

is a cyclopentadiene ligand; the coordination atom A is selected from boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium;

wherein the ligand group is selected from the following structures:

wherein the pendant hydrogen bonding group comprises at least one of the following structures represented by the following general formula:

wherein X is selected from oxygen atom, sulfur atom, silicon atom and nitrogen atom, and Y is selected from oxygen atom and sulfur atom;

a is R attached to the X atom ₂ The number of (2); when X is an oxygen atom or a sulfur atom, a is 0, R ₂ Is absent; when X is selected from nitrogen, a ═ 1; when X is a silicon atom, a ═ 2; r ₁ 、R ₂ Each independently selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group having a molecular weight of no more than 1000 Da;

j is a divalent linking group selected from the group consisting of single bonds, heteroatom linkers, divalent small molecule hydrocarbon groups having a molecular weight of no more than 1000 Da;

q is a terminal group selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group having a molecular weight of not more than 1000 Da;

it is shown as being linked to a polymer main chain skeleton, a cross-linked network chain skeleton, and a side chain.

2. Hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that the metal center is selected from the group consisting of ionic forms of metals, compound/chelate forms and combinations thereof.

3. Hybrid supramolecular acting dynamic polymer according to claim 2, characterized in that the ionic form of the metal is selected from the ionic forms of the following metals: cu, Ag, Au, Zn, Cd, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, La, Eu, Tb, Ho, Tm, Lu, Th.

4. Hybrid supramolecular acting dynamic polymer according to claim 2, characterized in that the compound/chelate form of the metal is selected from the following structures:

5. hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that the metal-ligand action is selected from the following structures:

6. hybrid supramolecular-acting dynamic polymer according to claim 1, characterized in that the heteroatoms are selected from nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, silicon atoms, boron atoms.

7. A hybrid supramolecular acting dynamic polymer as claimed in claim 1, characterized in that said pendant hydrogen bonding groups are selected from the following structures:

wherein m and n are the number of the repeating units and are fixed values, and both m and n are less than 5.

8. The hybrid supramolecular interaction dynamic polymer as claimed in claim 1, wherein said dynamic polymer further comprises at least one of backbone hydrogen bonding groups, terminal hydrogen bonding groups.

9. Hybrid supramolecular acting dynamic polymer according to claim 8, characterized in that the backbone hydrogen bonding group contains the following structural elements:

10. hybrid supramolecular acting dynamic polymer according to claim 9, characterized in that the backbone hydrogen bonding group contains the following structure:

11. hybrid supramolecular acting dynamic polymer according to claim 9, characterized in that the backbone hydrogen bonding group contains the following structure:

wherein,

refers to the linkage to a polymer chain backbone, a cross-linked network chain backbone.

12. Hybrid supramolecular acting dynamic polymer according to claim 9, characterized in that the backbone hydrogen bonding group is selected from the following structures:

13. hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that it is a non-crosslinked structure, wherein the degree of crosslinking of the metal-ligand action is below its gel point, the degree of crosslinking of the supramolecular hydrogen bonding action is below its gel point, and the sum of both degrees of crosslinking is lower than the gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

14. Hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that it is a crosslinked structure, wherein the degree of crosslinking of the metal-ligand action is below its gel point, the degree of crosslinking of the supramolecular hydrogen bonding action is below its gel point and the sum of the two degrees of crosslinking is above the gel point; wherein the hydrogen bond group containing the side group participates in the formed hydrogen bond action.

15. Hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that it is a crosslinked structure, wherein the degree of crosslinking of the metal-ligand action is below its gel point and the degree of crosslinking of the supramolecular hydrogen bonding action is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

16. Hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that it is a crosslinked structure wherein the degree of crosslinking for metal-ligand action is above its gel point and the degree of crosslinking for supramolecular hydrogen bonding is below its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

17. Hybrid supramolecular acting dynamic polymer according to claim 1, characterized in that it is a crosslinked structure wherein the degree of crosslinking of metal-ligand action is above its gel point and the degree of crosslinking of supramolecular hydrogen bonding is above its gel point; wherein the hydrogen bonding group containing side group participates in the formed hydrogen bonding action.

18. Hybrid supramolecular interaction dynamic polymer according to claim 1, characterized in that the formulation components constituting the dynamic polymer composition further comprise any one or several of the following additives: auxiliary agents and filling materials;

wherein, the added auxiliary agent is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, mold release agents, plasticizers, foaming agents, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, leveling agents, and antibacterial agents;

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

19. Hybrid supramolecular action dynamic polymer according to claim 1, characterized in that the topology of the polymer chains in the dynamic polymer or its composition and raw material ingredients is selected from the group consisting of linear, cyclic, branched, clustered, cross-linked and combinations thereof.

20. Hybrid supramolecular interaction dynamic polymer according to any of claims 1, 8, 13 to 19, characterized in that the morphology of the dynamic polymer or its composition has any of the following: solutions, emulsions, pastes, glues, gels, elastomers, foams.

21. Hybrid supramolecular acting dynamic polymer according to any of claims 1, 8, 13 to 19, characterized by its application in self-healing coatings, self-healing sheet materials, self-healing adhesives, sealing materials, tough materials, toy materials, stationery materials, shape memory materials, energy storage device materials, force sensor materials.