CN109206575A

CN109206575A - A kind of hybrid cross-linked dynamic aggregation object

Info

Publication number: CN109206575A
Application number: CN201710522384.7A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Iron Cloth Mstar Technology Ltd
Priority date: 2017-06-30
Filing date: 2017-06-30
Publication date: 2019-01-15

Abstract

A kind of hybrid cross-linked dynamic aggregation object, contains supermolecular mechanism and the covalent cross-linking formed by covalent bond, wherein more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network；Wherein, the supermolecular mechanism is at least selected from close metal function, halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, ion hydrogen bond action, radical cation dimerization.Characteristic and covalent cross-linking based on supermolecular mechanism assign the strength and stability of polymer, so that the dynamic aggregation object can be used as self-repair material, toughness material, sealing material, adhesive, force snesor material etc. and is widely applied.

Description

Hybrid cross-linked dynamic polymer

The technical field is as follows:

the invention relates to the field of intelligent polymers, in particular to a hybrid cross-linked dynamic polymer formed by covalent bonds and supermolecule action.

Background art:

a hybrid cross-linked network structure (e.g., an interpenetrating network structure) is one that is effective in improving polymer properties, and in a covalent interpenetrating network structure, in order to obtain sufficient toughness, it is often necessary to swell the first network (e.g., with a solvent or with a second network) to a large extent, and in use, to sacrifice the first network (irreversible cleavage of covalent bonds) to obtain irreversible toughness. The dynamic polymer of the covalent hybrid cross-linked network can not be repaired after being damaged, is lack of dynamic property and can not be effectively recycled, so that the performance and the application of the dynamic polymer are greatly limited.

The supramolecular interaction is a non-covalent interaction emerging in recent years, and can be reformed after being dissociated by an acting force, so that the self-repairing effect of the polymer is realized. In recent years, there have been articles reporting dynamic polymers prepared based on various supramolecular interactions, and non-covalently crosslinked dynamic polymers have made some progress in recent years. However, many reports only use supramolecular action alone to prepare dynamic polymers, without support of covalent cross-linked network, and the prepared dynamic polymers generally have poor mechanical properties, which greatly limits the application range of dynamic polymers.

Therefore, it is necessary to develop a new hybrid crosslinked dynamic polymer, which can provide the system with dimensional stability, good mechanical properties and excellent dynamic properties to solve the problems in the prior art.

Disclosure of Invention

Against the above background, the present invention provides a hybrid crosslinked dynamic polymer characterized in that it comprises covalent crosslinks formed by covalent bonds and at least one supramolecular interaction selected from the group consisting of metallophilic interactions, halogen bonding interactions, cationic-pi interactions, anionic-pi interactions, benzene-fluorobenzene interactions, ionic hydrogen bonding interactions, radical cationic dimerization; wherein the covalent crosslinks reach above the gel point of the covalent crosslinks in the at least one crosslinked network.

In an embodiment of the present invention, the hybrid crosslinked dynamic polymer optionally further comprises other supramolecular interactions, wherein the other supramolecular interactions include dipole-dipole interactions, hydrogen bonding interactions, metal-ligand interactions.

In the hybrid crosslinked dynamic polymers described in the present invention, the other supramolecular interactions may be intrachain non-crosslinking interactions and/or interchain crosslinking interactions and/or non-crosslinking interactions.

According to a preferred embodiment of the invention (first polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks provided by the supramolecular interactions is above or below its gel point.

According to another preferred embodiment of the present invention (second polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions and at least one other supramolecular interaction in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point, the degree of crosslinking of the supramolecular interactions provided by the supramolecular interactions is above or below its gel point, and the degree of crosslinking of the supramolecular interactions provided by the other supramolecular interactions is above or below its gel point.

According to another preferred embodiment (third polymer network structure) of the present invention, the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one of the cross-linked networks comprises both covalent cross-linking and supramolecular interaction, wherein the degree of cross-linking of the covalent cross-linking is above the gel point and the degree of cross-linking of the supramolecular interaction cross-linking provided by the supramolecular interaction is above or below the gel point; the other cross-linked network contains only at least one other supramolecular interaction, wherein the supramolecular cross-linking provided by the other supramolecular interaction has a degree of cross-linking above its gel point.

According to another preferred embodiment of the present invention (fourth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions, wherein the supramolecular interactions provide a degree of cross-linking of the supramolecular interactions above the gel point.

According to another preferred embodiment of the present invention (fifth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains a supramolecular effect, wherein the degree of cross-linking of the supramolecular effect cross-linking provided by the supramolecular effect is above the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction.

According to another preferred embodiment of the present invention (sixth polymer network structure), the hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network only contains supramolecular action, wherein the degree of cross-linking of the supramolecular action cross-linking provided by the supramolecular action is above the gel point; the third crosslinked network contains only at least one other supramolecular interaction, wherein the supramolecular interaction provides a degree of crosslinking above or below its gel point.

According to another preferred embodiment of the present invention (seventh polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions and covalent cross-links with a cross-linking degree above its gel point, wherein the supramolecular interactions provide supramolecular interactions with a cross-linking degree above or below its gel point.

According to another preferred embodiment of the present invention (eighth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular action and covalent cross-linking, and the cross-linking degree of the covalent cross-linking is higher than the gel point, wherein the cross-linking degree of the supramolecular action cross-linking provided by the supramolecular action is higher than or lower than the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction.

According to another preferred embodiment of the invention (ninth polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein non-crosslinked supramolecular polymers comprising supramolecular interactions are dispersed in the at least one network.

According to another preferred embodiment of the invention (tenth polymer network structure) the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein non-crosslinked supramolecular polymers comprising supramolecular interactions and at least one other supramolecular interaction.

According to another preferred embodiment of the present invention (eleventh polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein the crosslinked polymer comprising supramolecular interactions is dispersed in the form of particles in the at least one network.

According to another preferred embodiment of the invention (twelfth polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein the crosslinked polymer comprising supramolecular interactions and at least one other supramolecular interaction is dispersed in the at least one network in the form of particles.

According to another preferred embodiment of the present invention (thirteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and metallophilic interactions in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular interactions provided by the metallophilic interactions is above or below its gel point.

According to another preferred embodiment of the present invention (fourteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and benzene-fluorobenzene interaction in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above the gel point, and the degree of crosslinking of the supramolecular interaction crosslinks provided by the benzene-fluorobenzene interaction is above or below the gel point.

According to another preferred embodiment of the present invention (fifteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and ionic hydrogen bonding in the crosslinked network, wherein the degree of covalent crosslinks is above its gel point, and the degree of supramolecular crosslinks provided by ionic hydrogen bonding is above or below its gel point.

According to another preferred embodiment of the present invention (sixteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinking and halogen bonding in the crosslinked network, wherein the halogen bonding provides supramolecular bonding crosslinking with a degree of crosslinking above or below its gel point.

According to another preferred embodiment of the present invention (seventeenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and cation-pi interactions in the crosslinked network, the cation-pi interactions providing supramolecular interactions that crosslink at a degree of crosslinking above or below its gel point.

According to another preferred embodiment of the present invention (eighteenth polymer network structure), the hybrid crosslinked dynamic polymer contains only one crosslinked network, and contains both covalent crosslinking and anion-pi interaction in the crosslinked network, and the degree of crosslinking of the supramolecular interaction crosslinking provided by the cation-pi interaction is above or below its gel point.

According to another preferred embodiment of the present invention (nineteenth polymer network structure), the hybrid crosslinked dynamic polymer contains only one crosslinked network, and contains both covalent crosslinking and radical cationic dimerization in the crosslinked network, the degree of crosslinking of the supramolecular interaction crosslinks provided by the radical cationic dimerization being above or below its gel point.

In the embodiment of the present invention, the term "metallophilic" refers to when the two outermost electronic structures are d¹⁰Or d⁸When the metal ions are close to less than the sum of their van der Waals radii, an interaction force is generated, forming a metallophilic interaction.

In embodiments of the present invention, the halogen bond refers to a non-covalent interaction formed between a halogen atom or a lewis acid and a neutral or negatively charged lewis base.

In an embodiment of the present invention, the cation-pi interaction refers to a non-covalent interaction formed between a cation and a pi-electron system of an aromatic system.

In an embodiment of the present invention, the anion-pi interaction refers to a non-covalent interaction formed between an anion and an electron-deficient aromatic pi system.

In the present embodiment, the benzene-fluorobenzene reaction refers to a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon through the combination of dispersive force and quadrupole moment.

In the embodiment of the present invention, the ionic hydrogen bonding is composed of a positive ionic group and a negative ionic group capable of forming hydrogen bonding, and simultaneously forms hydrogen bonding and coulomb interaction between positive and negative ions, or is composed of a positive/negative ionic group and a neutral hydrogen bonding group capable of forming hydrogen bonding, and simultaneously forms hydrogen bonding and ion-dipole interaction between positive/negative ions and neutral groups.

In an embodiment of the present invention, the building blocks of the free radical cationic dimerization are groups containing both free radicals and cations.

In the embodiment of the present invention, the dipole-dipole effect refers to that when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction effect of the atom with the larger electronegativity, so that the electrons are asymmetrically distributed to generate an electric dipole, and the two electric dipoles interact to form the dipole-dipole effect.

In an embodiment of the present invention, the hydrogen bonding is formed by hydrogen bonding between hydrogen bonding groups present at any one or more of the dynamic polymer chain backbone (including side chains/branches/forked chains), side groups, and end groups. The hydrogen bonding group preferably contains the following structural elements:

more preferably at least one of the following structural components:

wherein,refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom.

In an embodiment of the invention, said metal-ligand interaction, said ligand group (represented by L) is selected from cyclopentadiene and a building block comprising 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 bonding of A to A by a single bond means that the coordinating atoms belong to the same ligand group, and when two or more coordinating atoms are contained in a ligand group, A is a single toothMay be the same atom or may be different atoms including, but not limited to, boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium, 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)_xRepresenting 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 embodiments of the present invention, the dynamic polymer may be in the form of a common solid, elastomer, gel (including hydrogel, organogel, oligomer-swollen gel, plasticizer-swollen gel, ionic liquid-swollen gel), foam, or the like.

In an embodiment of the present invention, a dynamic polymer comprising a combination of supramolecules, the raw material components constituting the dynamic polymer further comprise any one or more of the following additives: other polymers, auxiliaries, fillers;

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

wherein, the additive can be selected from any one or more of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, foaming agents, 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.

The hybrid crosslinked dynamic polymer described in the embodiments of the present invention is applied to the following articles: self-repairing material, sealing material, toughness material, adhesive, toy material, stationery material, shape memory material, force sensor material and energy storage device material.

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

(1) in the dynamic polymers of the invention, covalent crosslinking and at least one supramolecular interaction selected from the group consisting of metalphilic interactions, halogen bonding interactions, cationic-pi interactions, anionic-pi interactions, pi-pi stacking interactions, benzene-fluorobenzene interactions, ionic hydrogen bonding interactions, radical cationic dimerization interactions are present in one polymer system. The formation mode of the selected supermolecule action is rich, the supermolecule action has strong sensitivity to the external environment, and the dynamic polymer based on the supermolecule action has more sensitive dynamic performance such as the directionality of halogen bond action, the controllable selectivity and controllable identification of cation-pi action and anion-pi action, the orderliness of benzene-fluorobenzene action, the pH, concentration sensitivity and conductivity of ion hydrogen bond action, the special photoelectricity of metallophilic interaction and free radical cation dimerization and the like through regulation and control of the external environment, and supermolecule action groups/units can be reasonably selected according to requirements for molecular design. In addition, a strong and stable network structure is provided for the dynamic polymer through covalent crosslinking, the polymer can keep a balanced structure, the dynamic and static combination of supermolecule action and covalent bonds is realized, the synergistic action is shown in the polymer network, and enough toughness is provided for the crosslinked polymer, so that the crosslinked polymer has excellent tensile toughness and tear resistance while having the inherent mechanical strength and stability of the crosslinked structure.

(2) The dynamic polymer also contains other optional supermolecule actions, the advantages of the supermolecule actions are fully utilized and combined, the dipole-dipole action is sensitive to temperature, the preparation of a temperature response material can be realized, the acting force of the hydrogen bond action and the metal-ligand action is generally larger, the mechanical property of the dynamic polymer can be supplemented, meanwhile, the strength, the structure, the dynamic property, the responsiveness, the forming condition and the like of different series of supermolecule actions are different, the performance effects of synergy and orthogonality can be achieved, and the material can obtain the self-repairability, the plasticity and the reworkability of the orthogonality.

(3) The dynamic polymer of the invention has rich dynamic action and controllable effect. The dynamic property of the supermolecule effect can be specifically regulated and controlled through external conditions such as the pH value of the environment, the polarity of a solvent, the temperature, light waves, oxidation reduction or an electromagnetic field, so that the dynamic effect of the dynamic polymer is richer, the dynamic polymer with different response properties is prepared, and the application range of the polymer is expanded.

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 cross-linked dynamic polymer, characterized in that it comprises covalent cross-links formed by covalent bonds and at least one supramolecular action selected from the group consisting of metallophilic action, halogen bond action, cation-pi action, anion-pi action, benzene-fluorobenzene action, ionic hydrogen bonding action, radical cationic dimerization; wherein the covalent crosslinks reach above the gel point of the covalent crosslinks in the at least one crosslinked network.

The term "polymerization" reaction/action as used in the present invention, unless otherwise specified, refers to a chain extension process/action in which a lower molecular weight reactant forms a product having a higher molecular weight by polycondensation, polyaddition, ring opening polymerization, or the like. 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 product resulting from the polymerization of one reactant is called a homopolymer. The product resulting from the polymerization of two or more reactants is referred to as a copolymer. 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 as well as non-covalent interactions.

The term "crosslinking" reaction/action as used in the present invention, unless otherwise specified, refers to the process of chemical linkage between reactant molecules and/or covalent bonds within reactant molecules and the physical action of supramolecular action to form products having a two-dimensional, three-dimensional cluster and/or 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. When multiple cross-linking effects are present, in addition to covalent cross-linking reaching above its gel point in at least one network, other cross-linking effects may be above or below its gel point.

In embodiments of the present invention, there may be one or more than one covalent cross-linking, i.e., any suitable covalent cross-linking chemistry, topology, degree of cross-linking, and combinations thereof may be employed. In embodiments of the present invention, the crosslinked network may have at least one, i.e., a single network, multiple networks blended with each other, or multiple networks interpenetrating between the networks. In embodiments of the invention, however, the covalent crosslinks must reach above the gel point of the covalent crosslinks in at least one network. Thus, it is ensured that the polymer of the invention maintains an equilibrium structure even in the case of only one network, i.e.it can be insoluble and infusible in the usual state. In addition to covalently crosslinked networks, other crosslinked or non-crosslinked components may be included, including but not limited to polymers, small molecules, inorganic material components; wherein the topology of the polymer composition may include, but is not limited to, linear, branched, cyclic, clustered, cross-linked.

In embodiments of the present invention, supramolecular interaction is achieved by supramolecular interaction in any suitable location in the dynamic polymer including, but not limited to, the polymer backbone, side groups, end groups. Furthermore, intra-chain supramolecular interactions may be formed between supramolecular interacting groups in any position under certain conditions, such intra-chain supramolecular interactions do not directly produce cross-linking, but may lead to cross-linking if nested rings are produced. In addition, in the general case of the present invention, the supramolecular action provided by the skeletal supramolecular acting group can cause the polymer to form microphase separation under certain conditions, and the skeletal supramolecular action exists in the hard phase to form strong non-covalent crosslinking together with the hard phase, thereby playing a role in increasing the stability and mechanical strength of the equilibrium structure on one hand, and improving the toughness on the basis of the non-covalent characteristics thereof on the other hand. In the present invention, one or more than one same or different supramolecular interactions may be present in the same polymer chain/molecule/network, and the supramolecular interactions in any one network may be at any degree of cross-linking.

In the embodiment of the present invention, the skeletal supramolecular interaction group/unit refers to a group/unit in which at least one atom directly participates in the construction of a polymer backbone or a cross-linking linkage on a continuous polymer backbone or a cross-linking network backbone; the side group supermolecule interaction group/unit means that all atoms on the group/unit are on the side group; the terminal supramolecular interacting group/unit refers to the group/unit with all atoms on the terminal group. The skeletal supramolecular interacting groups/units may be generated during polymerization/cross-linking of the polymer, i.e. by formation of the supramolecular interacting groups/units; or may be previously formed and then polymerized/crosslinked; preferably generated in advance. The side group supramolecular interacting group/unit may be generated before, after or during polymerization/crosslinking, the amount generated before or after being relatively freely controllable.

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 a molecular weight of not more than 1000Da and a short side chain with a molecular weight of not more than 1000Da which are connected with the polymer main chain skeleton/crosslinking network main 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.

According to a preferred embodiment of the invention (first polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks provided by the supramolecular interactions is above or below its gel point. For this embodiment, which contains only one cross-linked network, covalent cross-linking in the system is used to provide a balanced structure, achieving dynamic effects through the dynamics of supramolecular interactions; and the preparation is more convenient.

According to another preferred embodiment of the present invention (second polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions and at least one other supramolecular interaction in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point, the degree of crosslinking of the supramolecular interactions provided by the supramolecular interactions is above or below its gel point, and the degree of crosslinking of the supramolecular interactions provided by the other supramolecular interactions is above or below its gel point. In this embodiment, by introducing other supramolecular interactions into the single cross-linked network structure, it can be used as a complement to the supramolecular interactions, allowing the polymer to exhibit a hierarchical dynamic reversible and orthogonal synergistic effect.

According to another preferred embodiment (third polymer network structure) of the present invention, the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one of the cross-linked networks comprises both covalent cross-linking and supramolecular interaction, wherein the degree of cross-linking of the covalent cross-linking is above the gel point and the degree of cross-linking of the supramolecular interaction cross-linking provided by the supramolecular interaction is above or below the gel point; the other cross-linked network contains only at least one other supramolecular interaction, wherein the supramolecular cross-linking provided by the other supramolecular interaction has a degree of cross-linking above its gel point. In the embodiment, independent other supramolecular interaction cross-linked networks are additionally introduced, so that the supramolecular interaction cross-linked networks can be used as a supplement to the dynamic property of the supramolecular interaction, and the polymer can show a hierarchical dynamic reversible effect.

According to another preferred embodiment of the present invention (fourth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions, wherein the supramolecular interactions provide a degree of cross-linking of the supramolecular interactions above the gel point. In the embodiment, the covalent cross-linking network is responsible for keeping a balanced structure, the network based on the supermolecule action is responsible for providing dynamic performance, and the covalent cross-linking network and the supermolecule action network can form an interpenetrating network or a semi-interpenetrating network, so that the advantages of the covalent cross-linking network and the supermolecule action network are fully utilized to achieve a synergistic and/or orthogonal dynamic effect.

According to another preferred embodiment of the present invention (fifth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains a supramolecular effect, wherein the degree of cross-linking of the supramolecular effect cross-linking provided by the supramolecular effect is above the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction. In the embodiment, the supramolecular interaction network and the covalent cross-linking network are not directly in the same network, and the dynamic regulation and control capability of the polymer is stronger and the synergistic effect is better due to the introduced other supramolecular interaction.

According to another preferred embodiment of the present invention (sixth polymer network structure), the hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network only contains supramolecular action, wherein the degree of cross-linking of the supramolecular action cross-linking provided by the supramolecular action is above the gel point; the third crosslinked network contains only at least one other supramolecular interaction, wherein the supramolecular interaction provides a degree of crosslinking above or below its gel point. In the embodiment, the supramolecular cross-linked network, other supramolecular cross-linked networks and the covalent cross-linked network respectively and independently exist, so that the dynamic polymer shows different orthogonality and cooperativity by utilizing the difference of the dynamic property and the stability between different cross-linked networks, and a better self-repairing effect is achieved.

According to another preferred embodiment of the present invention (seventh polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises only covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions and covalent cross-links with a cross-linking degree above its gel point, wherein the supramolecular interactions provide supramolecular interactions with a cross-linking degree above or below its gel point. In this embodiment, the structure of the two covalent cross-linked networks is controlled to achieve the purpose of reasonably regulating and controlling the equilibrium structure and mechanical properties of the dynamic polymer.

According to another preferred embodiment of the present invention (eighth polymer network structure), the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises covalent crosslinks and the degree of crosslinking of the covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular action and covalent cross-linking, and the cross-linking degree of the covalent cross-linking is higher than the gel point, wherein the cross-linking degree of the supramolecular action cross-linking provided by the supramolecular action is higher than or lower than the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction. In the embodiment, the purpose of reasonably regulating and controlling the balance structure and the mechanical property of the dynamic polymer can be achieved by controlling the structures of the two covalent cross-linked networks, and the dynamic regulation and control capability of the polymer can be stronger and the synergistic and self-repairing effects are better due to the introduced other supermolecule effects.

According to another preferred embodiment of the invention (ninth polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein non-crosslinked supramolecular polymers comprising supramolecular interactions are dispersed in the at least one network. When the non-crosslinked supramolecular polymer containing the supramolecular effect is subjected to an external force, the supramolecular effect can play a dynamic reversible effect, and the durability of the material is improved.

According to another preferred embodiment of the invention (tenth polymer network structure) the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein non-crosslinked supramolecular polymers comprising supramolecular interactions and at least one other supramolecular interaction. When the non-crosslinked supramolecular polymer containing the supramolecular effect and at least one other supramolecular effect is subjected to an external force, the supramolecular effect can play a dynamic reversible effect, the durability is improved, and the introduced other supramolecular effect can also enable the dynamic regulation and control capability of the polymer to be stronger, and the synergistic and self-repairing effects to be better.

According to another preferred embodiment of the present invention (eleventh polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein the crosslinked polymer comprising supramolecular interactions is dispersed in the form of particles in the at least one network. When the cross-linked polymer containing the supermolecule function existing in the particles is acted by external force, the supermolecule function can play a dynamic reversible effect, and the durability of the material is improved.

According to another preferred embodiment of the invention (twelfth polymer network structure), the dynamic polymer comprises at least one crosslinked network, wherein the at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein the crosslinked polymer comprising supramolecular interactions and at least one other supramolecular interaction is dispersed in the at least one network in the form of particles. When the cross-linked polymer containing the supermolecule effect and at least one other supermolecule effect existing in the particles is subjected to an external force, the supermolecule effect can play a dynamic reversible effect, the durability is improved, and the dynamic regulation and control capability of the polymer is stronger and the synergistic and self-repairing effects are better due to the introduced other supermolecule effect.

According to another preferred embodiment of the present invention (thirteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and metallophilic interactions in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular interactions provided by the metallophilic interactions is above or below its gel point. In the embodiment, the metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the dynamic property of the prepared polymer is more sufficient.

According to another preferred embodiment of the present invention (fourteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and benzene-fluorobenzene interaction in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above the gel point, and the degree of crosslinking of the supramolecular interaction crosslinks provided by the benzene-fluorobenzene interaction is above or below the gel point. In this embodiment, a dynamic polymer having a specific function can be prepared by utilizing reversibility of the benzene-fluorobenzene action and the stacking action.

According to another preferred embodiment of the present invention (fifteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and ionic hydrogen bonding in the crosslinked network, wherein the degree of covalent crosslinks is above its gel point, and the degree of supramolecular crosslinks provided by ionic hydrogen bonding is above or below its gel point. In this embodiment, the ionic hydrogen bond has strong sensitivity to pH, and the dynamic polymer dynamics can be adjusted by controlling the pH value in the system.

According to another preferred embodiment of the present invention (sixteenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinking and halogen bonding in the crosslinked network, wherein the halogen bonding provides supramolecular bonding crosslinking with a degree of crosslinking above or below its gel point. In this embodiment, the halogen bond has a wide variety of structures, and the structure and the dynamic properties of the dynamic polymer can be effectively adjusted by effectively designing the halogen bond donor and acceptor, and the ordered and self-repairing dynamic polymer can be designed based on the halogen bond effect.

According to another preferred embodiment of the present invention (seventeenth polymer network structure), the hybrid crosslinked dynamic polymer comprises only one crosslinked network, and contains both covalent crosslinks and cation-pi interactions in the crosslinked network, the cation-pi interactions providing supramolecular interactions that crosslink at a degree of crosslinking above or below its gel point. In the embodiment, the cation-pi action has rich types and moderate intensity, can stably exist in various environments, and can prepare dynamic polymers with rich performance based on the cation-pi action.

According to another preferred embodiment of the present invention (eighteenth polymer network structure), the hybrid crosslinked dynamic polymer contains only one crosslinked network, and contains both covalent crosslinking and anion-pi interaction in the crosslinked network, and the degree of crosslinking of the supramolecular interaction crosslinking provided by the cation-pi interaction is above or below its gel point. In this embodiment, the anion-pi interactions are reversible and controllably identifiable, enabling the construction of dynamic polymers with specific properties.

According to another preferred embodiment of the present invention (nineteenth polymer network structure), the hybrid crosslinked dynamic polymer contains only one crosslinked network, and contains both covalent crosslinking and radical cationic dimerization in the crosslinked network, the degree of crosslinking of the supramolecular interaction crosslinks provided by the radical cationic dimerization being above or below its gel point. In this embodiment, dynamic polymers with special functionalities can be prepared using the optoelectronic properties of free radical cationic dimerization.

The present invention may also have other various hybrid network structure embodiments, and one embodiment may have three or more networks that are the same or different, and those skilled in the art may reasonably and effectively implement the present invention according to the logic and context of the present invention.

In the embodiment of the present invention, the term "metallophilic" refers to when the two outermost electronic structures are d¹⁰Or d⁸The metal ions of (a) are brought into proximity to less than the sum of their van der waals radii to produce an interaction force, and the two metal ions that are metallophilic may be the same or different. The outermost electronic structure is d¹⁰Metal ions of (2) include, but are not limited to, Cu⁺、Ag⁺、Au⁺、 Zn²⁺、Hg²⁺、Cd²⁺Preferably of Au⁺、Cd²⁺(ii) a The outermost electronic structure is d⁸Metal ions of (2) include, but are not limited to, Co⁺、Ir⁺、Rh⁺、Ni²⁺、Pt²⁺、Pb²⁺Preferably Pt²⁺、Pb²⁺. The metallophilic effect can exist stably in the polymer, has moderate effect strength and certain directionality, and is not in useHas obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the prepared polymer has more sufficient dynamic property.

In the embodiment of the present invention, the combination of forming the metallophilic action is not particularly limited as long as a suitable metallophilic action is formed between metal ions. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

Cu—Cu、Ag—Ag、Au—Au、Zn—Zn、Hg—Hg、Cd—Cd、Co—Co、Ir—Ir、Rh—Rh、Ni—Ni、Pt—Pt、Pb—Pb、Cu—Ag、Cu—Au、Ag—Au、Cu—Zn、Cu—Co、Cu—Pt、Zn—Co、 Zn—Pt、Co—Pt、Co—Rh、Ni—Pb。

in the present embodiment, the halogen bonding refers to the non-covalent interaction between a halogen atom and a neutral or negatively charged lewis base, and the essence is the interaction between the sigma-anti bond orbital of the halogen atom and an atom or pi-electron system with a lone electron pair. Halogen bond interactions can be represented by-X.Y-, wherein X can be selected from Cl, Br, I, preferably Br, I; y can be selected from F, Cl, Br, I, N, O, S, pi bond, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on the halogen bond effect, ordered and self-repairing dynamic polymers can be designed.

In the embodiment of the present invention, the combination of the atoms forming the halogen bond function is not limited as long as a stable halogen bond function can be formed in the dynamic polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

—Cl···Cl—、—Cl···F—、—Cl···Br—、—Cl···I—、—Cl···N—、—Cl···O—、—Cl···S—、—Cl···π—、—Br···Br—、—Br···F—、—Br···I—、—Br···N—、—Br···O—、—Br···S—、—Br···π—、—I···I—、—I···F—、—I···N—、—I···O—、—I···S—、—I···π—。

in an embodiment of the present invention, the cation-pi interaction refers to a non-covalent interaction formed between a cation and a pi-electron system of an aromatic system. There are three main classes of cation-pi action, the first being simple inorganic cations or ionic groups (e.g. Na)⁺、K⁺、Mg²⁺、NH₄ ⁺、Ca²⁺) And aromatic systems; the second is the interaction between organic cations (e.g., quaternary ammonium cations) and fragrance systems; the third type is the interaction between positively charged atoms in the dipole bond (e.g., H atoms in an N-H bond) and the aromatic system. The cation-pi effect has rich varieties and moderate intensity, can stably exist in various environments, and can prepare dynamic polymers with rich performance based on the cation-pi effect.

In the embodiment of the present invention, the kind of the cation-. pi.function is not particularly limited as long as it can form a stable cation-. pi.function in the dynamic polymer. Some suitable cationic groups may be exemplified by, but are not limited to:

Na⁺、K⁺、Li⁺、Mg²⁺、Ca²⁺、Be²⁺、H-O、H-S、H-N。

in an embodiment of the present invention, the anion-pi interaction refers to a non-covalent interaction formed between an anion and an electron-deficient aromatic pi system. The anion may be a simple inorganic non-metallic ion or group of ions (e.g., Cl)^-、Br^-、 I^-、OH^-) (ii) a Or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system refers to the condition that the ring atoms are electronegativeThe difference in properties is that the distribution of pi electron clouds in the ring is not uniform, and pi electrons are mainly shifted to the electronegative high electron direction, thereby leading to the decrease of the distribution density of pi electron clouds in the aromatic ring, such as pyridine, fluorobenzene, etc. The anion-pi action has reversibility and controllable identification, and can be used for constructing dynamic polymers with special properties.

In the embodiment of the present invention, the kind of the anion- π action is not particularly limited as long as it can form a stable anion- π action in the dynamic polymer. Some suitable anions may be exemplified below, but the invention is not limited thereto:

Cl^-、Br^-、I^-、OH^-、SCN^-。

some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.

In the present embodiment, the benzene-fluorobenzene reaction refers to a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon through the combination of dispersive force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The reversibility and stacking effect of the benzene-fluorobenzene action are utilized to prepare the dynamic polymer with special functions.

In the embodiment of the present invention, the kind of the benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the dynamic polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:

In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:

in an embodiment of the present invention, the building blocks of the free radical cationic dimerization are groups containing both free radicals and cations. By way of example, the free radical cationic dimerization may be formed, including but not limited to the following:

in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:

in the embodiment of the present invention, the dipole-dipole effect refers to that when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction effect of the atom with the larger electronegativity, so that the electrons are asymmetrically distributed to generate an electric dipole, and the two electric dipoles interact to form the dipole-dipole effect. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ N, C-F, H-O, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effects may exhibit differences in dynamics depending on the temperature differences.

In the embodiment of the present invention, the combination between dipoles is not particularly limited as long as a suitable dipole-dipole action can be formed between the dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in an embodiment of the present invention, the hydrogen bonding, which is any suitable supramolecular interaction established by hydrogen bonding, is generally a hydrogen bond linkage between Z and Y mediated by hydrogen between the hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, to generate a Z-H … Y form, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, and may be selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably F, N, O atom, and more preferably O, N atom. The hydrogen bond function can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three. The present invention also does not exclude that the hydrogen bonds play a grafting role.

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 dynamics of the hydrogen bonding action is strong. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.

In embodiments of the invention, the hydrogen bonding may be effected by the presence of non-covalent interactions between any suitable hydrogen bonding groups. Wherein, the hydrogen bond group can only contain a hydrogen bond donor, only contain a hydrogen bond acceptor, or contain both the hydrogen bond donor and the hydrogen bond acceptor, preferably contain both the hydrogen bond donor and the hydrogen bond acceptor. Wherein, the hydrogen bonding group preferably comprises the following structural components:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein,refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom. In embodiments of the present invention, the hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, derivatives of the above, and the like.

In the present invention, said hydrogen bonding groups may be present only on the polymer chain backbone (including side chains/branches/bifurcations), referred to as backbone hydrogen bonding groups; or may be present only in pendant groups (also including multilevel structures of pendant groups), referred to as pendant hydrogen bonding groups; or may be present only on the polymer chain/small molecule end group, referred to as an end hydrogen bonding group; or may be present in at least two of the polymer chain backbone, the polymer chain pendant group, the polymer chain/small molecule end group. When present on at least two of the polymer chain backbone, the polymer chain pendant groups, and the polymer chain/small molecule end groups at the same time, hydrogen bonds may be formed between hydrogen bonding groups in different positions, in particular instances, for example, the backbone hydrogen bonding groups may form hydrogen bonds with the pendant hydrogen bonding groups.

Among these, suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):

among these, suitable pendant hydrogen bonding groups/terminal hydrogen bonding groups may have the above-mentioned skeleton hydrogen bonding group structure, and are exemplified by (but the invention is not limited to) the following:

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

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

In the invention, the dynamic property of the polymer can be combined, matched and regulated in a large range by controlling the type and the number of hydrogen bond groups on the polymer chain skeleton and/or the side group, and the dynamic polymer with richer structure, more diverse performance and more hierarchical dynamic reversible effect can be obtained based on the difference between the dynamic property and the action of various supermolecules.

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, including 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)_xRepresenting 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.

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 interaction₂Structure) 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 the number of teeth each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, and therefore, in the present invention, it is preferable that the ligand group 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:

examples of monodentate ligand groups are as follows:

-C≡N；

bidentate ligand groups are exemplified as follows:

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 compound which can provide a suitable metal center is preferably a chelate compound having a vacancy in a coordination site, or a chelate compound in which a part of the ligands can be substituted with the skeletal ligand 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 interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

in embodiments of the present invention, the generation or introduction of supramolecular interacting 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, which can be introduced before the ligand is formed, after the polymerization/crosslinking of the composition which forms the metal-ligand interaction with the ligand has been carried out, or after the polymerization/crosslinking has been completed. Preferably after ligand generation but before covalent cross-linking.

The invention has rich formation modes of selected supermolecule action and stronger sensitivity to the external environment, and can enable the dynamic polymer based on the supermolecule action to have more sensitive dynamic performance by regulating and controlling the external environment, such as the directionality of halogen bond action, the controllable selectivity and controllable identification of cation-pi action and anion-pi action, the orderliness of benzene-fluorobenzene action, the pH, concentration sensitivity and conductivity of ionic hydrogen bond action, the temperature sensitivity of dipole-dipole action, the special photoelectricity of metallophilic interaction and free radical cation dimerization, and the like, and can reasonably select supermolecule action groups/units to carry out molecular design according to requirements.

The process means of the above-mentioned "covalent crosslinking" may in principle be any suitable covalent crosslinking and means. Generally, the method comprises two modes, namely synthesizing linear or branched prepolymer and then carrying out interchain crosslinking reaction; or from monomers, crosslinking is achieved in one step or by reaction.

In embodiments of the present invention, the covalent crosslinks are any suitable covalent crosslinks established through covalent bonds, including but not limited to covalent crosslinks formed through carbon-carbon bonds, covalent crosslinks formed through carbon-sulfur bonds, covalent crosslinks formed through carbon-oxygen bonds, covalent crosslinks formed through carbon-nitrogen bonds, and covalent crosslinks formed through silicon-oxygen bonds. The covalent crosslinks in any one of the crosslinked network structures of the dynamic polymer may have at least one chemical structure, at least one degree of branching, and at least one type and means of reaction.

In embodiments of the present invention, covalent crosslinking may employ any suitable reaction, including but not limited to the following types: crosslinking by covalent reaction between carboxyl group, acid halide group, acid anhydride group, ester group, amide group, isocyanate group, epoxy group and hydroxyl group; crosslinking by covalent reaction between carboxyl group, acid halide group, acid anhydride group, ester group, amide group, isocyanate group, epoxy group and amino group; crosslinking through an olefin free radical reaction and an acrylate free radical reaction; covalent crosslinking is carried out through CuAAC reaction of azide groups and alkynyl and click reaction of sulfydryl and olefin; covalent crosslinking is carried out by condensation reactions between the silicon hydroxyl groups.

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 "organic group" as used herein means a group mainly composed of a carbon element and a hydrogen element as a skeleton, and may be a small molecular group having a molecular weight of not more than 1000Da or a polymer chain residue having a molecular weight of more than 1000Da, and suitable groups include, for example: methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde, acetyl, acetonyl, and the like.

The 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 indicated number of carbon atoms, e.g. C_1-4An alkyl group including alkyl groups having 1,2,3, or 4 carbon atoms in a linear or branched arrangement. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl, decyl.

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

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

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

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

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

the heterocyclic structure mentioned refers to a cyclic structure containing at least one heteroatom in the cyclic structure, such as:

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 a hydrogen atom, also e.g. -CH₂-CH₂-CH₂-is replaced by-CH₂-S-CH(CH₃)-。

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

In the embodiment of the present invention, the form of the dynamic polymer or its composition may be normal solid, hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel, ionic liquid swollen gel, elastomer, foam material, etc., wherein the content of soluble small molecular weight component in normal solid and foam material is generally not higher than 10 wt%, and the content of small molecular weight component in gel is generally not lower than 50 wt%. 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. Elastomers have the general properties of ordinary solids, but at the same time have better elasticity and are softer. The gel has good flexibility, can show better rebound resilience, and is preferably a gel swelled by plasticizer, oligomer, ionic liquid and organic solvent with boiling point higher than that of water. The foam material has the advantages of low density and lightness, can overcome the problems of brittleness of partial common solid and low mechanical strength of gel, 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 to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.

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

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

Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the dynamic polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into 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 the bubble nucleation stage, after materials are added into a screw, the materials are heated and rubbed to be changed into a melt state, a foaming agent is injected into the material melt at a certain flow rate through the control of a metering valve, and then the foaming agent is uniformly mixed by a mixing element at the head of the screw to form bubble nuclei under the action of a nucleating agent. The expansion stage and the solidification shaping stage are both carried out after the die cavity is filled, when the pressure of the die cavity is reduced, the expansion process of the bubble nucleus occurs, and 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.

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

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

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

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

During the preparation process of the dynamic polymer, certain other polymers, auxiliaries and fillers which can be added to jointly form the dynamic polymer material, but the additives are not necessary.

The other polymers can be used as additives to improve material performance, endow materials with new performance, improve material use and economic benefits and achieve the effect of comprehensive utilization of 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 or copolymer according to the difference of polymerization form, and the polymer is selected according to the performance of the target material and the requirement of the actual preparation process in the specific using process.

When the other polymer is selected from natural high molecular compounds, it can be selected from any one or several of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, 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, polyacrylamide, polyacrylonitrile, polybenzimidazole, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene terephthalate, Acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenol resin, urea resin, unsaturated polyester, polyisoprene, polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, polychloroprene, isobutylene-isoprene copolymer, polyorganosiloxane, vinylidene fluoride-chlorotrifluoroethylene copolymer, epichlorohydrin-ethylene oxide copolymer, 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.

Catalysis in the additiveAn agent capable of accelerating the reaction rate of reactants during the reaction by changing the reaction pathway and reducing the activation energy of the reaction, which includes, but is not limited to, ① a catalyst for polyurethane synthesis, which includes 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 ' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, etc., an organometallic catalyst such as octylic acid, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctanoate, lead isooctanoate, potassium octoate, triethylamine, potassium octoate, potassium naphthenate, potassium aluminum chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride, potassium chloride, sodium chloride₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, etc., ④ thiol-ene reaction catalyst, photocatalyst, such as benzoin dimethyl ether, 2-hydroxy-2-methylphenyl acetone, 2-dimethoxy-2-phenyl acetophenoneEtc.; 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 of the additive which can be added is capable of causing the monomer molecules to activate during the polymerization reaction to generate radicals, thereby increasing the reaction rate and promoting the reaction, and includes, but is not limited to, ① radical polymerization initiators such as organic peroxides, e.g., lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylperoxypivalate, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, azo compounds, e.g., Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides, e.g., ammonium persulfate, potassium persulfate, etc., ② living polymerization initiators such as 2,2,6, 6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine ternary system, etc., ③ ionic polymerization initiators such as butyllithium, sodium/naphthalene system, boron trifluoride/water system, tin tetrachloride/haloalkane system, ④ coordination system such as aluminum chloride/cuprous chloride/bipyridine chloride/tris-carboxylate system, preferably, 2. 7. the ring-opening polymerization initiators such as sodium chloride/stannous chloride/aluminum chloride/bis (ethylene-benzoyl) system, 3. the preferred polymerization initiators are no.

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

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, dimethyl tin isooctyl dimercaptoacetate, dimethyl tin dimercaptolate, and combinations thereof; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; polyols, such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; 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 usually 0.1 to 0.5% by weight.

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

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 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, so that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation at break, flexibility and flexibility are improved, and the plasticizer comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. 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_5～9Acid ethylene glycol ester, C_5～9Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyesters, 1, 2-propanediol sebacic acid polyesters; 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 alkylsulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate ester diethanolamine salts, potassium p-nonylphenyl ether sulfonates, phosphate ester derivatives, phosphates, polyoxyethylene alkyl ether alcohol phosphates, phosphate ester derivatives, fatty amine sulfonates, sodium butyrate sulfonates; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium ethyl inner salt, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine ethyl inner salt, N-lauryl-N, N-dipolyoxyethylene-N-ethylphosphonic acid sodium salt, N-alkyl amino acid salts; nonionic antistatic agents such as fatty alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene phosphoric acid ether esters, glycerin 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. Among them, the dispersant is preferably sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (dispersant N) and fatty alcohol-polyoxyethylene ether, and the amount of the dispersant used is not particularly limited, and is generally 0.3 to 0.8 wt%.

The colorant in the additive can make the polymer product present the required color and increase the surface color, and the colorant includes but is not limited to any one or several of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. lithol rubine BK, lake Red C, perylene Red, Jia-base R Red, Phthalocyanine Red, permanent magenta HF3C, Plastic scarlet R and Clomomor Red BR, permanent orange HL, fast yellow G, Ciba Plastic yellow R, permanent yellow 3G, permanent yellow H₂G. Phthalocyanine blue B, phthalocyanine green, plastic purple RL and aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil-soluble yellow, etc. The 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 series such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as high chlorine content chlorinated paraffins, 1,2, 2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorendic anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like. Among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and antimony trioxide are preferable as the flame retardant, 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, ethylene propylene rubber, ethylene propylene diene monomer and the like. Among them, the nucleating agent is preferably silica, dibenzylidene sorbitol (DBS) or ethylene propylene diene monomer, 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 emulsions, acrylic copolymers, polyvinyl alcohol, polyethylene wax, and the like. Among them, organobentonite, polyethylene wax, hydrophobically modified alkali swellable emulsion (HASE) and Alkali Swellable Emulsion (ASE) are preferable, and the amount of the rheology agent to be used is not particularly limited, but is usually 0.1 to 1% by weight.

The thickening agent in the additive can endow the polymer mixed solution with good thixotropy and proper consistency, thereby meeting the requirements of various aspects such as stability and application performance during production, storage and use, and the like, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, 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, fine powder silica, colloidal aluminum, plant polysaccharides, microbial polysaccharides, animal proteins, alginic acids, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyether, and polyvinylmethylether urethane polymer. Of these, coconut oil diethanolamide and acrylic acid-methacrylic acid copolymer are preferable as the thickener, and the amount of the thickener used is not particularly limited, but is generally 0.1 to 1.5% by weight.

The leveling agent in the additive can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the leveling agent comprises any one or more of the following leveling agents: polyacrylates, silicone resins, and the like. Among them, the leveling agent is preferably polyacrylate, 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%.

① reduces the shrinkage rate of a molded product, improves the dimensional stability, surface smoothness, flatness or dullness of the product, ② adjusts the viscosity of the material, ③ meets different performance requirements, 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, ④ improves the coloring effect of the pigment, ⑤ endows the product with light stability and chemical corrosion resistance, ⑥ plays a role in compatibilization, can reduce the cost and improve the competitiveness of the product in the market.

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, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, carbon nano tubes, fullerene, molybdenum disulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, white mud, alkali mud, boron mud, (hollow) glass microbeads, foamed microspheres, foamable particles, glass powder, cement, synthetic inorganic rubber, synthetic inorganic fibers, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, carbon-silicon fibers, ceramic fibers, whiskers 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)₂O₃、CoFe₂O₄、NiFe₂O₄、MnFe₂O₄、Fe₃O₄、FeN、Fe₂N、ε-Fe₃N、Fe₁₆N, 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 but is not limited to any one or any several of the following: fur, natural rubber, synthetic organic fiber, cotton linter, hemp, jute, flax, asbestos, shellac, lignin, protein, enzyme, hormone, raw lacquer, wood flour, shell flour, xylose, silk, rayon, vinylon, phenol-formaldehyde microbeads, resin microbeads, and the like.

The type of the filler to be added is not limited, but depends on the required material properties, and calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass beads, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, natural rubber, protein, and resin beads are preferred, and the amount of the filler to be 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, expandable particles, 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.

The method for producing the composition of the present invention is not particularly limited, and for example, the additive and the prepolymer may be blended as necessary by a roll, a kneader, an extruder, a universal mixer, or the like, and then subjected to subsequent operations such as crosslinking, foaming, or the like.

Due to the supermolecule effect with good dynamic performance formed by the ion-dipole action groups/units, the obtained dynamic polymer has certain modulus, toughness and self-repairing performance, and can be widely applied to elastic components and the like in adhesives, coatings, films and structural composite materials.

The hybrid crosslinked dynamic polymer gel material provided by the invention is preferably a water-soluble gel material, an organic solvent type gel material and a plasticizer swelling gel material, and more preferably a plasticizer swelling gel.

The preparation method of the dynamic polymer hydrosol type gel material comprises the following steps: for hydrophilic monomers, raw materials (including molecules containing ligands, metal centers, chain extenders, cross-linking agents, various auxiliaries and the like) of a hybrid cross-linked dynamic polymer are added into an aqueous solution, the mass fraction of the prepared hybrid cross-linked dynamic polymer (according to the embodiment of the invention, either a single-network dynamic polymer or an interpenetrating-network dynamic polymer) is 0.5-50%, covalent cross-linking is carried out by a proper means, and after the reaction is finished, natural cooling is carried out, so that a dynamic polymer hydrogel is prepared, namely a gel material is prepared by a one-step method; or preparing a polymer chain network containing the ligand, swelling the polymer chain network in an aqueous solution, adding the metal center, and removing the excess aqueous solution after the gelation reaction. The water solution is deionized water.

The invention relates to a preparation method of a dynamic polymer organic solvent type gel material, which comprises the following steps: for a monomer with poor hydrophilicity, adding raw materials of a hybrid cross-linked dynamic polymer into a proper organic solvent to ensure that the mass fraction of the prepared hybrid cross-linked dynamic polymer is 0.5-50%, carrying out covalent cross-linking by a proper means, and naturally cooling after the reaction is finished to prepare the dynamic polymer organic solvent type gel material, namely the gel material is prepared by a one-step method; or preparing a polymer chain network containing the ligand, swelling the polymer chain network in a proper organic solution, adding the metal center, and taking out the polymer chain network after the gelation reaction to remove the redundant organic solvent. The organic solvent is one or more of acetone, butanone, N-dimethylformamide, chloroform, dichloromethane, dimethyl sulfoxide, tetrahydrofuran, methanol, absolute ethyl alcohol, diethyl ether, N-pentane and toluene.

The invention relates to a preparation method of a dynamic polymer plasticizer swelling gel material, which comprises the following steps: adding a raw material with a hybrid cross-linked dynamic polymer into a proper plasticizer to enable the mass fraction of the prepared hybrid cross-linked dynamic polymer to be 0.5-50%, carrying out covalent cross-linking by a proper method, and naturally cooling after the reaction is finished to prepare a gel swelled by the dynamic polymer plasticizer, namely preparing a gel material by a one-step method; alternatively, the network of polymer chains containing the ligand may be prepared by swelling it in a suitable plasticizer, adding the metal centre, and removing the excess plasticizer after the gelling reaction. The plasticizer is selected from any one or more of the following components: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. 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_5～9Acid ethylene glycol ester, C_5～9Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester;polyesters such as 1, 2-propanediol ethanedioic acid polyesters, 1, 2-propanediol sebacic acid polyesters; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like. The epoxidized soybean oil is an environment-friendly plastic plasticizer with excellent performance and is prepared by performing epoxidation reaction on refined soybean oil and peroxide. It is volatile resistant, not easy to migrate and not easy to dissipate in polyvinyl chloride products. This is beneficial for maintaining the light and heat stability and extending the useful life of the article. Epoxidized soybean oil is extremely toxic and has been approved by many countries for use in food and pharmaceutical packaging materials, and is the only epoxy plasticizer approved by the U.S. food and drug administration for use in food packaging materials. In the preparation of a dynamic polymer plasticizer swollen gel of the present invention, the plasticizer is preferably epoxidized soybean oil.

In an embodiment of the present invention, the oligomer includes, but is not limited to: epoxy acrylate, modified epoxy acrylate, epoxy linseed oil triacrylate, polyester acrylate prepolymer, polyether acrylate, urethane acrylate prepolymer, tripropylene glycol methoxy ether monoacrylate, methoxy ether neopentyl glycol propoxy monoacrylate, methoxy ether trimethylolpropane ethoxy diacrylate, amine modified acrylate, liquid paraffin, polymer with number average molecular weight less than 10000; preferably epoxy acrylates, polyester acrylates, polyether acrylate prepolymers, polyureas, polycarbonates, polyesters, polyethers or polyamides having a number average molecular weight of less than 10000.

In an embodiment of the present invention, the ionic liquid includes, but is not limited to: imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid, piperidine ionic liquid, alkenyl functionalized ionic liquid, hydroxyl functionalized ionic liquid, ether group functionalized ionic liquid, ester group functionalized ionic liquid, carboxyl functionalized ionic liquid, nitrile group functionalized ionic liquid, amino functionalized ionic liquid, sulfonic acid functionalized ionic liquid, benzyl functionalized ionic liquid and guanidine ionic liquid; the concrete preference is selected from: 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-2, 3-dimethylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bromide, N-octylpyridinium bromide, tributylmethylammonium chloride, tetrabutylphosphonium bromide, N-butyl-N-methylpyrrolidine bromide, N-butyl-N-methylpiperidine bromide, 1-vinyl-3-butylimidazolium hexafluorophosphate, 1, 2-dimethyl-3-hydroxyethylimidazolium p-methylbenzenesulfonate, 1-ethylether-3-methylimidazolium hexafluorophosphate, 1-carbethoxy-3-methylimidazolium hexafluorophosphate, 1-carboxyethyl-3-methylimidazolium bromide, 1-hexyl-2, 3-dimethylimidazolium hexafluorophosphate, 1-cyanopropyl-3-methylimidazolium hexafluorophosphate, 1-aminopropyl-3-methylimidazolium hexafluorophosphate, butylpyridinium trifluoromethanesulfonate N-sulfonate, 1-benzyl-3-methylimidazolium tetrafluoroborate, tetramethylguanidium trifluoromethanesulfonate.

The hybrid crosslinked dynamic polymer foam material provided by the invention can be flexible, semi-rigid or rigid foam. The foam can be prepared under the condition of water or no water, and the foaming method can be one or more of physical foaming, chemical foaming and mechanical foaming. Further, the foam may use suitable auxiliary type non-reactive blowing agents known in the art.

The preparation method of the dynamic polymer foam material comprises the following steps: when preparing the single-network dynamic polymer foam material, a reaction material component A and a reaction material component B are prepared respectively and independently; the reaction material component A is prepared by uniformly stirring 8 to 20 parts of polyol compound, 0.05 to 1.0 part of chain extender, 0.05 to 1.0 part of cross-linking agent, 0.01 to 0.5 part of organic metal catalyst and 0.01 to 0.5 part of amine catalyst at the material temperature of 5 to 35 ℃ and the stirring speed of 50 to 200 r/min; the reaction material component B is prepared by uniformly stirring 10 to 20 parts of polyisocyanate compound, 0.5 to 3.5 parts of foaming agent and 0.05 to 0.2 part of foam stabilizer at the material temperature of 5 to 35 ℃ and the stirring speed of 50 to 200 r/min; and then mixing the reaction material component A and the reaction material component B according to the mass ratio of 1.0-1.5: 1, and quickly stirring by using professional equipment to obtain the foamed single-network dynamic polymer. And finally, adding the foamed single-network dynamic polymer into a mold, curing for 30-60 min at room temperature, and then curing at high temperature to obtain the dynamic polymer foam material based on the single network. At least one of the component A and the component B contains ligand groups. The high-temperature curing is performed for 6 hours at the temperature of 60 ℃, or for 4 hours at the temperature of 80 ℃, or for 2 hours at the temperature of 120 ℃. The molar ratio of hydroxyl (OH) groups in the polyol compound to isocyanate (NCO) groups in the polyisocyanate compound described above may be such that the final polyurethane foam is free of free terminal NCO groups. The molar ratio NCO/OH is preferably from 0.9/1 to 1.2/1. The NCO/OH molar ratio of 1/1 corresponds to an isocyanate index of 100. In the case of water as blowing agent, the isocyanate index is preferably greater than 100, so that the isocyanate groups can react with water.

In the preparation method of the dynamic polymer foam material, when the binary hybrid cross-linked dynamic polymer foam material is prepared, according to the steps of preparing the single-network dynamic polymer, the 1 st network is prepared; then in the process of preparing the 2 nd network, adding the 1 st network into a reaction material A ', namely the reaction material component A' comprises 8 to 20 parts of polyol compound, 0.05 to 1 part of chain extender, 0.05 to 0.4 part of cross linker, 0.01 to 0.5 part of organic metal catalyst, 0.01 to 0.5 part of amine catalyst and 0.1 to 15 parts of 1 st network polymer, and uniformly stirring at the material temperature of 5 to 35 ℃ and the stirring speed of 50 to 200r/min to obtain the catalyst; the reaction material component B' is 10 to 20 portions of polyisocyanate compound, 2 to 3.5 portions of foaming agent and 0.05 to 0.2 portion of foam stabilizer, and is prepared by uniformly stirring at the stirring speed of 50 to 200r/min at the material temperature of 5 to 50 ℃. And then mixing the reaction material component A 'and the reaction material component B' according to the mass ratio of 1.0-1.5: 1, and quickly stirring by using special equipment to obtain the foamed hybrid cross-linked dynamic polymer. And finally, adding the foamed hybrid crosslinked dynamic polymer into a mold, curing at room temperature for 30-60 min, and then curing at high temperature to obtain the hybrid crosslinked dynamic polymer-based foam material. At least one of the component A 'and the component B' contains ligand groups. The high-temperature curing is performed for 6 hours at the temperature of 60 ℃, or for 4 hours at the temperature of 80 ℃, or for 2 hours at the temperature of 120 ℃. By analogy, when the ternary hybrid cross-linked dynamic polymer foam material is prepared, the 1 st network and the 2 nd network are prepared, and then the 1 st network and the 2 nd network are added to be fully mixed for foaming when the 3 rd network is prepared.

In the preparation process of the hybrid crosslinked 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 condition and the target polymer performance.

The dynamic polymer foam material provided by the invention also relates to: converting the dynamic polymeric foam material into any desired shape, such as tubes, rods, sheaths, containers, spheres, sheets, rolls, and tapes, by welding, gluing, cutting, routing, perforating, embossing, laminating, and thermoforming; use of the dynamic polymer foam in a floating device; combining the dynamic polymeric foam material with sheets, films, foams, fabrics, reinforcements, and other materials known to those skilled in the art into a complex sandwich structure by lamination, bonding, fusing, and other joining techniques; use of the dynamic polymer foam in a gasket or seal; use of the dynamic polymer foam in a packaging material or in a container. With respect to the dynamic polymers of the present invention, the foamable dynamic polymers are of a type such that they can be deformed by extrusion, injection molding, compression molding or other forming techniques known to those skilled in the art.

The dynamic polymer of the invention has covalent cross-linking above gel point and good dynamic performance pi-pi stacking effect, and the obtained dynamic polymer has certain stability and self-repairing performance. Covalent cross-linking maintains well the equilibrium structure of the dynamic polymer, while at the same time it can act as a sacrificial bond to increase the toughness of the material due to the presence of supramolecular interactions. For example, through proper component selection and formula design, the polymer plugging rubber with good plasticity can be prepared; based on the dynamic reversibility of the supermolecule effect, the material with shape memory and self-repairing functions and the polymer film, the fiber or the plate with excellent toughness can be designed and prepared, and the material has wide application in the fields of biomedical materials, military, aerospace, energy, buildings and the like; in addition, by utilizing the dynamic property, a sensor sensitive to stress and the like can be prepared.

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

Example 1

Adding 100 parts by mass of toluene, 36 parts by mass of acrylamide, 7.2 parts by mass of 1H,1H, 2H-heptafluoropentane-1-ene, 0.1 part by mass of azobisisobutyronitrile and 0.01 part by mass of Tetramethylethylenediamine (TEMED) into a No. 1 reactor, stirring and mixing uniformly, heating to 80 ℃, reacting for 2 hours, adding 24 parts by mass of Toluene Diisocyanate (TDI), continuing to react for 2 hours, removing the solvent, washing with deionized water as much as possible, then putting the product into 100 parts by mass of deionized water, and swelling for 12 hours at room temperature to obtain the dynamic polymer hydrogel. The gel is prepared into a dumbbell-shaped sample bar 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 measured sample tensile strength is 1.12 +/-0.15 MPa, the elongation at break is 245.21 +/-23.17%, and the gel can be prepared into a self-adhesive drug-loaded flexible gel material for use.

Example 2

Dissolving 1 molar equivalent of polyacrylonitrile (average molecular weight is about 10000), 5 molar equivalents of 3- (azidomethyl) pyridine, 10 molar equivalents of 2, 5-dehydration-1-azido-1-deoxy-D-glucitol, 3 molar equivalents of azido methyl acetate, 100 molar equivalents of zinc chloride, 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 and 1, 6-hexamethylene diisocyanate with 0.5 time of molar equivalent of the sum of hydroxyl groups in dimethyl sulfoxide to obtain a cross-linked modified polyacrylonitrile product 2; adding a DMSO solution containing ferric trifluoromethanesulfonate into a proper amount of the modified polyacrylonitrile product 2, uniformly stirring, standing and swelling for 12h to obtain the dynamic polymer organogel. The organogel 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 3

36 parts by mass of 3-buten-1-ol, 7.8 parts by mass of allylurea-2-fluorene (obtained by reacting 2-aminofluorene with allyl isocyanate), 2.3 parts by mass of sodium acrylate, 0.1 part by mass of potassium persulfate (KPS), 0.12 part by mass of N, N-Dimethylformamide (DMF), 150mL of dimethyl sulfoxide DMSO (DMSO) were added to a reactor No. 1, and the mixture was stirred at room temperature for reaction for 1 hour, adding 3 parts by mass of nickelocene polymer, uniformly mixing, adding 60 parts by mass of diphenylmethane diisocyanate (MDI) and 0.7 part by mass of triethylamine, uniformly mixing, heating to 60 ℃, reacting for 2 hours, removing the solvent, washing the product with deionized water, and then placing the gel into a mixed solution of 100 parts by mass of ethylene phthalate and 2 parts by mass of pyridine for standing and swelling for 24 hours to obtain the dynamic polymer plasticizer swelling gel. The plasticizer swelling gel can show different mechanical properties according to the action speed of external force, shows the effect of shock hardening, has good toughness and self-repairability, and can be used for manufacturing a tough material for use.

Example 4

Adding 0.3 molar equivalent of allyl carbamate-6-anthrylene (prepared by reacting 6-hydroxymethyl anthrylene with allyl isocyanate), 1 molar equivalent of methacryloyl trimethyl ammonium chloride, 0.005 molar equivalent of potassium persulfate (KPS), 0.005 molar equivalent of N, N-dimethyl cyclohexylamine and sufficient dichloromethane into a No. 1 reactor, heating to 50 ℃, stirring for reaction for 4 hours, and removing the solvent to obtain a product 1; mixing and dissolving 50 parts by mass of product 1, 35 parts by mass of acrylamide, 0.5 part by mass of AIBN and 0.5 part by mass of TEMED in 100 parts by mass of toluene, heating to 80 ℃ for reaction for 2 hours, adding 40 parts by mass of TDI, continuing to react for 2 hours, removing the solvent, washing with deionized water, adding 5 parts by mass of graphene and 50 parts by mass of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, performing ultrasonic dispersion, uniformly stirring, standing for 24 hours, and removing the solvent to obtain the dynamic polymer ionic liquid swelling gel. The ionic liquid swelling gel has good conductivity and mechanical property, and can be prepared into a super capacitor with self-repairing property for use.

Example 5

Adding 10 parts by mass of methyl acrylate, 5.5 parts by mass of 3-allyl-5-methyl-1H-pyrrolo [2,3-b ] pyridine, 0.12 part by mass of methyl ethyl ketone peroxide, 0.12 part by mass of 4-dimethylaminopyridine and 180 parts by mass of chloroform into a No. 1 reactor, stirring and reacting for 1H at room temperature, adding 50 parts by mass of Tetrahydrofuran (THF), continuously stirring for 12H, and then washing THF with deionized water as much as possible to obtain a product 1; adding 10 parts by mass of product 1, 10 parts by mass of polyethylene glycol (the molecular weight is about 1000) and 20 parts by mass of dichloromethane into a No. 2 reactor, completely dissolving and mixing, adding 5 parts by mass of polymethylene polyphenyl polyisocyanate, 0.2 part by mass of triethylamine, 0.1 part by mass of copper chloride and 0.5 part by mass of glass beads, after ultrasonic dispersion, heating to 80 ℃, continuing to react for 2 hours, adding 30 parts by mass of alkyl-terminated polyethylene glycol oligomer and 0.5 part by mass of cadmium chloride, uniformly mixing, removing the solvent, placing the blend in a mold, keeping the temperature at 80 ℃ for 12 hours, and cooling to obtain the dynamic polymer oligomer swelling gel. The product is made into a dumbbell-shaped sample bar 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 4.42 plus or minus 0.79MPa, the elongation at break is 213.43 plus or minus 32.74 percent, and the product can be made into the self-repairing sealing material with good sealing effect.

Example 6

Adding 1 molar equivalent of hydrogen-containing silicone oil (the average molecular weight is about 20000, the molar ratio of the repeating unit containing the silicon and the repeating unit without the silicon and the hydrogen is about 1:2) and 15 molar equivalents of allyl urea and quaternary ammonium hydroxide accounting for 7 percent of the total mass of the silicone oil into a No. 1 reactor, fully mixing, placing in a mold, heating to 170 ℃, preserving heat for 10 minutes, and cooling to obtain a product 1; adding 1 molar equivalent of hydrogen-containing silicone oil (the average molecular weight is about 20000, the molar ratio of the repeating unit containing the silicon and the repeating unit without the silicon and the hydrogen is about 1:2), 25 molar equivalents of acrylonitrile, 2 molar equivalents of (perfluorohexyl) ethylene and 7 percent of quaternary ammonium base of the total mass of the silicone oil into a No. 2 reactor, fully mixing, placing in a mold, heating to 170 ℃, preserving heat for 10 minutes, and cooling to obtain a product 2; 20 parts by mass of a product 1, 15 parts by mass of a product 2, 10 parts by mass of hydrogen-containing silicone oil (the average molecular weight is about 20000, the molar ratio of a repeating unit containing silicon and a repeating unit containing no silicon and hydrogen is about 1:2), 2 parts by mass of crosslinking agent divinyl terminated silicone oil and quaternary ammonium hydroxide accounting for 7% of the total mass of the silicone oil are fully mixed and placed in an internal mixer for mixing, 1 part by mass of carbon black and 1 part by mass of glass fiber are added, and after mixing for 6 hours, the mixture is taken out and placed in a mold and cooled to obtain the dynamic polymer elastomer. The product has good strength and plasticity, and can be prepared into products with different shapes according to the size of the mould. After the elastomer is cut off, good pressure is applied to the cross section for 1-2h, and the cross section can be bonded automatically and reshaped. The road speed bump can be applied to a road speed bump by utilizing the functional characteristics of the road speed bump. Under the action of the tensile force, the synergistic effect between the dipole-dipole effect and the hydrogen bond effect ensures that the tensile strength and the elongation at break of the dynamic polymer are improved to a certain extent, and the mechanical property is better. When the material is at a higher temperature, the dipole-dipole effect of the material is weakened, the synergistic effect is reduced, and the dynamic polymer can show orthogonal mechanical effect at different temperatures.

Example 7

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 reactor No. 1, dissolving the mixture in sufficient toluene, stirring the mixture until the mixture is dissolved and mixed uniformly, adding 0.4 time of carboxyl molar equivalent of 2,3,4,5, 6-pentafluoroaniline and 0.4 time of carboxyl molar equivalent of aniline, continuously stirring the mixture at room temperature for reaction for 12 hours, adding 0.2 time of carboxyl molar equivalent of 1, 4-diaminobutane, continuously reacting for 6 hours, and removing the solvent to prepare a product 1 for later use; 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. 2 reactor, dissolving in sufficient toluene, stirring until the mixture is dissolved and mixed uniformly, adding 0.5-time carboxyl molar equivalent of 1, 4-diaminobutane, continuously stirring at room temperature for 12h, and removing the solvent to prepare a product 2; mixing 30 parts by mass of the product 1, 20 parts by mass of the product 2 and 50 parts by mass of polyether ketone, adding 3 parts by mass of glass fiber and 1 part by mass of nano talcum powder, and carrying out extrusion granulation and injection molding to obtain the common dynamic polymer solid. A dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by 2.0mm is taken, a tensile testing machine is utilized to carry out tensile test, the tensile rate is 10mm/min, the tensile strength of the sample is 67.53 +/-6.25 MPa, the elongation at break is 57.56 +/-5.63%, the sample can be made into a self-repairing plate for use by utilizing the surface hardness and the high strength of the sample, and the surface scratches can be automatically repaired and healed.

Example 8

Adding 5.6 parts by mass of 4-bromo-1-butene, 8.4 parts by mass of 3-buten-1-ol, 15 parts by mass of ethyl acrylate, 0.5 part by mass of azobisisobutyronitrile and 0.1 part by mass of TEMED into a No. 1 reactor, uniformly stirring, heating to 90 ℃, continuing to react for 4 hours, adding 4 parts by mass of TDI and 0.05 part by mass of triethylamine, and continuing to react for 2 hours to obtain a product 1; adding 100 parts by mass of polyether polyol SA-460 (hydroxyl value 445-475) and 17 parts by mass of isopropyl isocyanate into a No. 2 reactor, heating to 80 ℃, reacting for 1h, heating to 100 ℃, and reacting for 2h to obtain a product 2; 20 parts by mass of a product 1, 100 parts by mass of a product 2, 1 part by mass of diethyltoluenediamine (DETDA), 0.5 part by mass of dibutyltin dilaurate (DY-12), 50 parts by mass of TDI, 4 parts by mass of water, 2 parts by mass of dichloromethane, 0.5 part by mass of carbon nanotubes and 5 parts by mass of graphene are dispersed by ultrasonic waves, placed in a proper mold, uniformly mixed by a professional stirrer, heated to 80 ℃ for reaction and foaming, and the foam is placed in a 60 ℃ oven for continuous curing for 6 hours after foaming is completed, so that a dynamic polymer foam material is prepared, the dynamic polymer foam material is prepared into a block sample with the size of 20.0 x 20.0mm, a compression performance test is carried out by using a universal testing machine, the compression rate is 2mm/min, and the 10% compression strength of the sample is 6.34 +/-0.63 MPa. The obtained polymer foam material has light specific gravity, good strength and easy molding, and can be used as an antistatic layer of an electronic device.

Example 9

In reactor No. 1,1 mol equivalent of sodium alginate is dissolved in sufficient deionized water, and then 0.5 mol equivalent of NaIO is added₄Stirring at room temperature in a dark place for 6h, adding 0.5 molar equivalent of ethylene glycol, continuously stirring for 1h, dialyzing, and performing rotary evaporation to obtain sodium alginate with the theoretical oxidation degree of about 50%, adding 1.5 parts by mass of sodium alginate with the theoretical oxidation degree of about 50% into a sufficient amount of PBS buffer solution in a No. 2 reactor, adding 6.2 parts by mass of β -guanidinopropionic acid, continuously stirring for 6h, stirring and mixing, placing the mixed solution into a 20 ℃ thermostat, standing for 12h to obtain a product 1, adding 10 parts by mass of the product 1, 10 parts by mass of polyacrylamide (molecular weight 1000), 3 parts by mass of 1, 6-hexamethylene diisocyanate and 0.1 part by mass of triethylamine into the No. 2 reactor, uniformly mixing, heating to 80 ℃, and performing reverse evaporation at 80 DEG CAnd (3) reacting for 2 hours, adding 50 parts by mass of deionized water after the reaction is finished, and standing the mixed solution in a thermostat at 20 ℃ for 12 hours to obtain the dynamic polymer hydrogel. The dynamic polymer hydrogel has good toughness, is prepared into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by 2.0mm, is subjected to tensile test by using a tensile testing machine, has the tensile rate of 50mm/min, has the measured sample tensile strength of 2.53 +/-0.58 MPa and the elongation at break of 569.32 +/-78.35 percent, and can be prepared into an adhesive with self-repairing performance for use.

Example 10

In reactor No. 1,1 mol equivalent of sodium alginate is dissolved in sufficient deionized water, and then 0.5 mol equivalent of NaIO is added₄Stirring at room temperature in a dark place for 6h, adding 0.5 molar equivalent of glycol, continuously stirring for 1h, and dialyzing and rotary-steaming to obtain sodium alginate with a theoretical oxidation degree of about 50%; adding 5.5 parts by mass of sodium alginate with the theoretical oxidation degree of about 50% into a reactor No. 2, dissolving the sodium alginate in sufficient PBS buffer solution, adding 2.6 parts by mass of methylguanidine and 4.4 parts by mass of 3-bromopropylamine, continuously stirring for 6 hours, adding 0.1 part by mass of calcium chloride and 10 parts by mass of deionized water, stirring and mixing, and placing the mixed solution into a thermostat at 20 ℃ for standing for 12 hours to obtain a product 1; adding the prepared product 1, 100 parts by mass of polyether polyol EP-3600 (hydroxyl value is 26-30), 0.3 part by mass of N, N' -diethylpiperazine, 2 parts by mass of ethylenediamine (DA), 0.3 part by mass of dibutyltin dilaurate (DY-12), 1 part by mass of organic silicone oil, 9 parts by mass of isophorone diisocyanate, 5 parts by mass of water and 4 parts by mass of dichloromethane into a No. 3 reactor, uniformly mixing, heating to 80 ℃, quickly stirring for reaction by using a professional stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foam forming, 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 50% compression strength of the sample is 2.91 plus or minus 0.53 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, and can be made into a thermal insulation materialThe rows are used.

Example 11

Adding 1 molar equivalent of 3-buten-1-ol, 1 molar equivalent of acrylonitrile, 1 molar equivalent of 4-bromo-1-butene, 0.01 molar equivalent of potassium persulfate and 0.01 molar equivalent of TEMED into a reactor No. 1, adding sufficient toluene to stir and dissolve the mixture, then heating to 50 ℃, after reacting for 4 hours, adding 87 mass parts of TDI and 0.1 mass part of triethylamine, continuing to react for 2 hours, and removing the solvent to obtain a product 1; adding 100 parts by mass of polyether polyol EP-330N (hydroxyl value is 32-36), 30 parts by mass of product 1,3 parts by mass of foaming microspheres, 0.5 part by mass of N-ethylmorpholine, 8 parts by mass of MDI, 3 parts by mass of water and 3 parts by mass of dichloromethane into a No. 2 reactor, uniformly mixing, heating to 80 ℃, rapidly stirring and reacting by using a special stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 5.41 plus or minus 0.95 MPa. The obtained polymer foam material has light specific gravity, good rebound resilience and easy molding, and can be made into automotive interior materials for use.

Example 12

Adding 1 molar equivalent of polyether ketone powder with a carboxyl-containing side group, 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 reactor No. 1, dissolving in sufficient toluene, stirring until the mixture is dissolved and mixed uniformly, adding 0.3 time carboxyl molar equivalent of 3-aminopropionic acid ethyl ester, continuously stirring at room temperature for reaction for 12h, then adding 0.4 time carboxyl molar equivalent of aminobenzene and 0.3 time carboxyl molar equivalent of 1-pentafluorophenyl-2-thiourea, continuously reacting for 12h, and removing the solvent to obtain a product 1 for later use; 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. 2 reactor, dissolving in sufficient toluene, stirring until the mixture is dissolved and mixed uniformly, adding 0.5-time carboxyl molar equivalent of 1, 4-diaminobutane, continuously stirring at room temperature for 12h, and removing the solvent to prepare a product 2; mixing 10 parts by mass of the product 1 and 50 parts by mass of the product 2, adding 3 parts by mass of glass fiber and 3 parts by mass of carbon fiber, and performing 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 taken, a tensile testing machine is utilized to carry out tensile test, the tensile rate is 10mm/min, the tensile strength of the sample is 41.34 +/-2.45 MPa, the elongation at break is 85.32 +/-7.92%, the sample can be made into a self-repairing plate by utilizing the surface hardness and the high strength of the sample, and the surface scratch can be automatically repaired and healed.

Example 13

Adding 1 molar equivalent of [ 6-phenyl-2, 2' -bipyridyl ] -4-carboxylic acid, 1 molar equivalent of allyl isocyanate and 0.01 molar equivalent of triethylamine into a No. 1 reactor, fully dissolving in sufficient toluene, heating to 80 ℃, reacting for 2 hours, and removing the solvent to obtain a compound 1; mixing 5 parts by mass of compound 1 and 0.2 part by mass of NaOH, dissolving in 10 parts by mass of DMSO (dimethylsulfoxide), adding 30 parts by mass of ethyl acrylate in an ice bath, introducing nitrogen to remove oxygen, adding 0.02 part by mass of potassium persulfate, 0.01 part by mass of TEMED, 0.01 part by mass of platinum chloride and 0.5 part by mass of glass fiber, rapidly stirring and mixing, heating to 60 ℃, reacting for 4 hours, and removing the solvent to obtain the 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 4.42. + -. 0.73MPa and an elongation at break of 368.32. + -. 52.63%. The product can be prepared into a tough elastomer material for use.

Example 14

Adding 100 parts by mass of polyether polyol EP-560 (hydroxyl value 290-310) into a No. 1 reactor, heating to 80 ℃, adding 7.2 parts by mass of (iodomethyl) ethylene oxide and 0.1 part by mass of sodium hydroxide, heating to 100 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1, 0.5 part by mass of bis (2-dimethylaminoethyl) ether, 2 parts by mass of MOCA, 0.4 part by mass of DY-300, 0.8 part by mass of silicone oil, 30 parts by mass of MDI, 4 parts by mass of water, 7 parts by mass of foaming microspheres and 4 parts by mass of dichloromethane into a No. 4 reactor, uniformly mixing, heating to 80 ℃, quickly stirring and reacting by using a professional stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 50 percent compression strength of the sample is 3.58 +/-0.48 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, and can be made into stationery materials for use.

Example 15

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 2,3,4,5, 6-pentafluorobenzyl alcohol with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacted for 2 hours to obtain a compound 1; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, uniformly mixing, adding 1 molar equivalent of benzyl alcohol, heating to 80 ℃, stirring and reacting for 2 hours to obtain a compound 2; adding 100 parts by mass of polyether polyol EP-3600 (hydroxyl value is 26-30), 3.7 parts by mass of compound 1 and 2.7 parts by mass of compound 2 into a No. 4 reactor, heating to 80 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of triethylamine, 3 parts by mass of ethylenediamine (DA), 0.5 part by mass of modified triethylenediamine solution (DY-8154), 1 part by mass of silicone oil, 5 parts by mass of water, 4 parts by mass of dichloromethane and 4 parts by mass of MDI into a No. 5 reactor, uniformly mixing, heating to 80 ℃, quickly stirring and reacting by using a professional stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 3.12 +/-0.34 MPa. The obtained polymer foam material has light specific gravity, soft texture and good rebound resilience, and can be made into an automotive interior material for use.

Example 16

Adding 1 molar equivalent of vinyl-containing silicone oil, 0.01 molar equivalent of antioxidant 168, 5 molar equivalent of trimethyl (2-mercaptoethyl) ammonium, 5 molar equivalent of 4-mercaptopyridine and 10 molar equivalent of toluene into a No. 1 reactor, uniformly mixing, placing the mixture under 300W ultraviolet rays and the like for irradiation for 30min, taking out the mixture, and removing the solvent to obtain a product 1; and (2) taking 20 parts by mass of the product 1,3 parts by mass of the AC foaming agent, 1 part by mass of barium stearate and 2 parts by mass of foamable particles, mixing for 30min on an open mill, taking out the mixed rubber material, putting the mixed rubber material into a proper mould, and carrying out foaming molding by using a flat vulcanizing machine, wherein the molding temperature is 140-150 ℃, the molding 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. 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 1.87 +/-0.35 MPa. The obtained polymer foam material has light specific gravity and good elasticity, has the characteristic of slow rebound due to a semi-open and semi-closed pore structure, and can be prepared into a cloth doll filling material for use.

Example 17

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 2-iodoacetamide with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacted for 2 hours to obtain a compound 1; adding 100 parts by mass of polyether polyol EP-553 (hydroxyl value is 54-58) and 10 parts by mass of compound 1 into a No. 2 reactor, heating to 80 ℃, reacting for 1 hour, adding 2 parts by mass of ethyl isocyanate, and continuously reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of triethanolamine, 3 parts by mass of 1, 4-Butanediol (BDO), 0.5 part by mass of organic bismuth (DY-20), 1 part by mass of silicone oil, 3 parts by mass of water, 7 parts by mass of dichloromethane and 5 parts by mass of MDI into a No. 3 reactor, uniformly mixing, heating to 80 ℃, rapidly stirring and reacting by using a professional stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 a universal tester, the compression rate is 2mm/min, and the 50 percent compression strength of the sample is 3.42 +/-0.66 MPa. The obtained polymer foam material has light specific gravity, soft texture and good rebound resilience, and can be used as a luggage material.

Example 18

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 2,4, 6-trimethylbenzyl alcohol with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacted for 2 hours to prepare a compound 1; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, uniformly mixing, adding 1 molar equivalent of 7-amino-3-methyl-3, 4-dihydro-1H-benzo [ e ] [1,4] diazepine-2, 5-dione, heating to 80 ℃, and stirring for reacting for 2 hours to obtain a compound 2; adding 100 parts by mass of polyether polyol HPOP40 (hydroxyl value is 20-23), 3.2 parts by mass of compound 1 and 4.3 parts by mass of compound 2 into a No. 3 reactor, heating to 80 ℃, reacting for 1 hour, adding 1.5 parts by mass of 2, 3-epoxypropyltrimethylammonium chloride and 0.01 part by mass of sodium hydroxide, heating to 100 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of N, N-dimethylbenzylamine, 3 parts by mass of trimethylolpropane, 0.5 part by mass of dibutyltin dilaurate (DY-12), 1 part by mass of organic silicone oil, 4 parts by mass of water, 6 parts by mass of dichloromethane and 7 parts by mass of MDI into a No. 6 reactor, uniformly mixing, heating to 80 ℃, quickly stirring and reacting by using a professional stirrer, continuously curing the foam in a 60 ℃ oven for 6 hours after foaming and forming, and cooling to obtain the dynamic polymer foam material. 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 sample having a 50% compressive strength of 4.67. + -. 0.52 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, and can be made into a shape memory foam material for use.

Example 19

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, pyridazine-3-methanol with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacts for 2 hours to obtain a compound 1; adding 100 parts by mass of polyether polyol EP-455S (hydroxyl value is 43.5-46.5) and 3.3 parts by mass of compound 1 into a No. 3 reactor, heating to 80 ℃, reacting for 1 hour, adding 1.5 parts by mass of ethylene oxide potassium carboxylate and 0.01 part by mass of sodium hydroxide, heating to 100 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1, 0.5 part by mass of triethylamine, 3 parts by mass of Diethylaminoethanol (DEAE), 0.5 part by mass of organic bismuth (DY-20), 1.3 parts by mass of organic silicone oil, 3 parts by mass of water, 4 parts by mass of dichloromethane and 5 parts by mass of isophorone diisocyanate (IPDI) into a No. 4 reactor, uniformly mixing, heating to 80 ℃, quickly stirring and reacting by using a special stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 50% compression strength of the sample is measured to be 4.31 +/-0.56 MPa. The obtained polymer foam material has light specific gravity and good rebound resilience, and can be used as a foam sealing material.

Example 20

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 2, 3-dibromo-1-propanol with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacted for 2 hours to obtain a compound 1; adding 100 parts by mass of polyether polyol ED-28 (hydroxyl value is 26.5-29.5) and 3.7 parts by mass of compound 1 into a No. 3 reactor, heating to 80 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of N, N-dimethylcyclohexylamine, 2 parts by mass of ethylenediamine (DA), 0.5 part by mass of DY-215, 1 part by mass of silicone oil, 6 parts by mass of water, 7 parts by mass of dichloromethane and 4 parts by mass of 1, 6-Hexamethylene Diisocyanate (HDI) into a No. 5 reactor, uniformly mixing, heating to 80 ℃, quickly stirring and reacting by using a special stirrer, placing foam into a 60 ℃ oven for continuous curing for 6 hours after foaming and forming, 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 1.13 +/-0.21 MPa. The obtained polymer foam material has light specific gravity, soft texture and good rebound resilience, and can be made into a filling material in a cloth doll toy for use.

Example 21

1, 4-butanediisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after the temperature is raised to 80 ℃,1 molar equivalent of piperazine-1-formamidine is slowly added dropwise while stirring, and the reaction is continued for 1 hour after the dropwise addition is finished, so that a compound 1 is prepared; adding 1 molar equivalent of 1, 4-butyldiisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, heating to 80 ℃, slowly dropwise adding 1 molar equivalent of pyridine-4-methanol while stirring, and continuously reacting for 2 hours after dropwise adding is finished to obtain a compound 2; 100 parts by mass of polyether polyol DD-380A (hydroxyl value of 360-400), 0.5 part by mass of triethylamine, 37 parts by mass of compound 1 and 34 parts by mass of compound 2 are added into a No. 3 reactor, and after the temperature is raised to 80 ℃, after continuously reacting for 2 hours, adding 5 parts by mass of AC foaming agent, 10 parts by mass of sorbitol, 5 parts by mass of [2,3,5, 6-tetra { (diethylamino) methyl } phenylene-1, 4-bis (palladium trifluoromethanesulfonate) ], 34 parts by mass of TDI and 1 part by mass of ruthenium heterobenzene, heating to 80 ℃, after fully reacting and crosslinking, taking out a crosslinked product into a mold, carrying out foam molding by using a flat vulcanizing machine, wherein the mould pressing temperature is 140-150 ℃, the mould pressing time is 10-15min, and the pressure is 10MPa, so that the dynamic polymer foam material is finally obtained, and 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 sample 10% compressive strength of 17.45. + -. 1.53 MPa. The obtained polymer foam material has light specific gravity and good dimensional stability, and can be used as a tank underwater buoyancy material.

Example 22

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 2- (hydroxymethyl) anthracene with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacts for 2 hours to prepare a compound 1; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, uniformly mixing, adding 1 molar equivalent of 2,3,4,5, 6-pentafluorobenzyl alcohol, heating to 80 ℃, stirring and reacting for 2 hours to obtain a compound 2; adding 100 parts by mass of polyether polyol DL-400 (hydroxyl value 270-290) and 0.5 part by mass of triethylamine into a No. 3 reactor, uniformly mixing, adding 38 parts by mass of a compound 1, 18 parts by mass of a compound 2 and 17 parts by mass of isopropyl isocyanate, heating to 80 ℃, and continuously reacting for 2 hours to obtain a product 1; adding the prepared product 1, 100 parts by mass of polyether polyol MN-3050DF (hydroxyl value is 54-57), 5 parts by mass of 3-amino-1, 2-propylene glycol, 15 parts by mass of epoxidized soybean oil, 5 parts by mass of KH550, 70 parts by mass of kaolin, 2 parts by mass of glass fiber, 1 part by mass of fumed silica, 4 parts by mass of UV-531, 10 parts by mass of pentachlorophenol and 2 parts by mass of dibutyltin dilaurate into a reactor No. 4, uniformly mixing, adding 50 parts by mass of MDI, uniformly stirring, placing the mixed solution into a mold, standing in an oven at 50 ℃ for 4 hours, taking out and cooling to obtain the dynamic polymer elastomer material. The resulting product 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 18.34. + -. 1.23MPa and an elongation at break of 325.23. + -. 67.35%. The product can be prepared into a road deceleration strip for use, and the effect of automatic repair can be realized when the road deceleration strip is damaged and cracked. Under the action of the tensile force, the synergistic effect between the benzene-fluorobenzene action and the hydrogen bond action ensures that the tensile strength and the elongation at break of the dynamic polymer are improved to a certain extent; when the product is in a polar solvent, the hydrogen bonding effect is weakened, the mechanical property of the polymer is reduced, and in a polar solvent environment, the benzene-fluorobenzene effect and the hydrogen bonding effect present an orthogonal mechanical effect.

Example 23

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 3-aminopropionitrile with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacted for 2 hours to obtain a compound 1; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, uniformly mixing, adding 1 molar equivalent of 2- (hydroxymethyl) naphthalene, heating to 80 ℃, stirring and reacting for 2 hours to obtain a compound 2; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 3 reactor, uniformly mixing, adding 1 molar equivalent of 2,3,4,5, 6-pentafluorobenzyl alcohol, heating to 80 ℃, and stirring for reacting for 2 hours to obtain a compound 3; adding 100 parts by mass of polyether polyol EP-8000 (hydroxyl value is 22-26) and 0.5 part by mass of triethylamine into a No. 4 reactor, uniformly mixing, adding 3.7 parts by mass of a compound 1, 19 parts by mass of a compound 2 and 9 parts by mass of a compound 3, heating to 80 ℃, and continuously reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of N, N-dimethylcyclohexylamine, 2 parts by mass of triethylene glycol and 4 parts by mass of TDI into a No. 5 reactor, uniformly mixing, heating to 80 ℃, reacting for 2 hours, taking out the reaction liquid, placing the reaction liquid into a mold, adding 100 parts by mass of diisooctyl phthalate (DIOP), standing and swelling in a 30 ℃ oven for 24 hours, and thus obtaining the dynamic polymer plasticizer swelling gel. The gel has good toughness and pressure resistance, and can be made into a sealing material for use.

Example 24

The preparation method comprises the steps of taking 1 molar equivalent of 4,4' -azobis (4-cyanopentanol) as an initiator, taking 4-penten-1-ol as a chain transfer agent, taking stannous octoate as a catalyst, initiating ring-opening polymerization of α -chloro-epsilon-caprolactone by 50 molar equivalents, at 110 ℃, to obtain a product 1, dissolving the obtained product 1 in dimethylformamide, adding 2 molar equivalents of sodium azide of chlorine atoms, reacting to obtain a product 2, adding 0.6 molar equivalent of azido groups of bipyridinium iodide with one end being alkynyl and 0.2 molar equivalent of azido groups of 1, 4-diacetylene in tetrahydrofuran, reacting at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain a product 3, adding 2-5 mass parts of antioxidant 168 into 100 mass parts of the obtained product 3, fully blending, placing in a mold, and performing compression molding to obtain the dynamic polymer elastomer.

Example 25

Adding 150mL of N-methylpyrrolidone and 3g of graphene oxide into a reactor No. 1, adding 4.6g of 4, 4-diaminodiphenyl ether (ODA), 2.4g of 2-bromoethylamine and 2.4g of 5-aminouracil after ultrasonic dispersion is uniform, heating to 80 ℃, stirring and mixing uniformly, transferring the reactant into a hydrothermal reaction container, placing the hydrothermal reaction container in an oven at 80 ℃ for reaction for 24 hours, dispersing the prepared modified graphene oxide in the N-methylpyrrolidone by using ultrasonic after the reaction is finished, and preparing into a solution of 3.5mg/mL for later use; adding 72mL of N-methylpyrrolidone, 3.2g of 4, 4-diaminodiphenyl ether (ODA) and 6.3mL of modified graphene oxide solution into a No. 2 reactor, uniformly dispersing by using ultrasonic waves, adding 4.8g of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) in a nitrogen atmosphere, stirring until the mixture is completely dissolved, adding 13mL of acetic anhydride and 10.5mL of pyridine, uniformly mixing, immediately transferring reactants into a mold for manufacturing a film, and reacting for 24 hours to obtain the dynamic polymer film. The specimen was cut into a dumbbell-shaped specimen having a size of 80.0X 10.0X (0.08. + -. 0.02) mm, and subjected to a tensile test using a tensile tester at a tensile rate of 50mm/min to obtain a specimen having a tensile strength of 7.53. + -. 0.73MPa and an elongation at break of 275. + -. 45%. And recovering the sample after the sample is pulled off, putting the sample into a mold for attaching for 1-3h, and then forming a film again for repeated use, wherein the sample can be used as a recyclable antistatic film by utilizing the property of the sample.

Example 26

1, 6-hexamethylene diisocyanate with 1 molar equivalent and triethylamine with 0.01 molar equivalent are added into a reactor No. 1, after uniform mixing, 3-iodopropanol with 1 molar equivalent is added, the temperature is raised to 80 ℃, and the mixture is stirred and reacts for 2 hours to obtain a compound 1; adding 1 molar equivalent of 1, 6-hexamethylene diisocyanate and 0.01 molar equivalent of triethylamine into a No. 2 reactor, uniformly mixing, adding 1 molar equivalent of 3-hydroxypropionitrile, heating to 80 ℃, stirring and reacting for 2 hours to obtain a compound 2; adding 100 parts by mass of polyether polyol EP-8000 (hydroxyl value is 22-26) and 0.5 part by mass of triethylamine into a No. 4 reactor, uniformly mixing, adding 3.5 parts by mass of a compound 1 and 7.2 parts by mass of a compound 2, heating to 80 ℃, and reacting for 2 hours to obtain a product 1; adding the prepared product 1,1 part by mass of N, N-dimethylcyclohexylamine, 2 parts by mass of triethylene glycol and 4 parts by mass of TDI into a No. 5 reactor, uniformly mixing, heating to 80 ℃, reacting for 2 hours, taking out the reaction liquid, placing the reaction liquid into a mold, adding 100 parts by mass of diisooctyl phthalate (DIOP), standing and swelling in a 30 ℃ oven for 24 hours, and thus obtaining the dynamic polymer plasticizer swelling gel. The gel has good toughness and pressure resistance, and can be made into a sealing material for use.

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

Claims

1. Hybrid cross-linked dynamic polymer comprising covalent cross-links formed by covalent bonds and at least one supramolecular interaction selected from the group consisting of metallophilic interactions, halogen-bonding interactions, cationic-pi interactions, anionic-pi interactions, benzene-fluorobenzene interactions, ionic hydrogen bonding interactions, radical cationic dimerization; wherein the covalent crosslinks reach above the gel point of the covalent crosslinks in the at least one crosslinked network.

2. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer further comprises other supramolecular interactions including dipole-dipole interactions, hydrogen bonding interactions, metal-ligand interactions.

3. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions in the crosslinked network, wherein the degree of crosslinking of the covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks provided by the supramolecular interactions is above or below its gel point.

4. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and supramolecular interactions and at least one other supramolecular interaction in the crosslinked network, wherein the degree of covalent crosslinks is above its gel point, the degree of supramolecular crosslinks provided by the supramolecular interactions is above or below its gel point, and the degree of supramolecular crosslinks provided by the other supramolecular interactions is above or below its gel point.

5. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, one of which comprises covalent crosslinks and supramolecular interactions, wherein the degree of covalent crosslinks is above the gel point and the degree of supramolecular interactions crosslinks provided by the supramolecular interactions is above or below the gel point; the other cross-linked network contains only at least one other supramolecular interaction, wherein the supramolecular cross-linking provided by the other supramolecular interaction has a degree of cross-linking above its gel point.

6. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, one of which comprises only covalent crosslinks and the degree of covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions, wherein the supramolecular interactions provide a degree of cross-linking of the supramolecular interactions above the gel point.

7. The hybrid crosslinked dynamic polymer of claim 1, wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, one of which comprises covalent crosslinks and the degree of covalent crosslinks is above its gel point; the other cross-linked network contains a supramolecular effect, wherein the degree of cross-linking of the supramolecular effect cross-linking provided by the supramolecular effect is above the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction.

8. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises three crosslinked networks, one of which comprises only covalent crosslinks and the degree of covalent crosslinks is above its gel point; the other cross-linked network only contains supramolecular action, wherein the degree of cross-linking of the supramolecular action cross-linking provided by the supramolecular action is above the gel point; the third crosslinked network contains only at least one other supramolecular interaction, wherein the supramolecular interaction provides a degree of crosslinking above or below its gel point.

9. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, one of which comprises only covalent crosslinks and the degree of covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular interactions and covalent cross-links with a cross-linking degree above its gel point, wherein the supramolecular interactions provide supramolecular interactions with a cross-linking degree above or below its gel point.

10. The hybrid crosslinked dynamic polymer of claim 1, wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, one of which comprises covalent crosslinks and the degree of covalent crosslinks is above its gel point; the other cross-linked network contains supramolecular action and covalent cross-linking, and the cross-linking degree of the covalent cross-linking is higher than the gel point, wherein the cross-linking degree of the supramolecular action cross-linking provided by the supramolecular action is higher than or lower than the gel point; and at least one other supramolecular interaction is contained in at least one cross-linked network, wherein the cross-linking degree of the supramolecular interaction cross-linking provided by the other supramolecular interaction is higher than or lower than the gel point of the supramolecular interaction.

11. The hybrid crosslinked dynamic polymer according to claim 1, wherein the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein non-crosslinked supramolecular polymers comprising supramolecular interactions.

12. The hybrid crosslinked dynamic polymer according to claim 1, wherein the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein a non-crosslinked supramolecular polymer comprising supramolecular interactions and at least one other supramolecular interaction.

13. The hybrid crosslinked dynamic polymer according to claim 1, wherein the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein a crosslinked polymer comprising supramolecular interactions in the form of particles.

14. The hybrid crosslinked dynamic polymer according to claim 1, wherein the dynamic polymer comprises at least one crosslinked network, wherein at least one crosslinked network comprises covalent crosslinks above the gel point, and wherein at least one network has dispersed therein a crosslinked polymer comprising supramolecular interactions and at least one other supramolecular interaction in the form of particles.

15. The hybrid crosslinked dynamic polymer of claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and metallophilic interactions in the crosslinked network, wherein the degree of covalent crosslinks is above its gel point and the degree of supramolecular interactions crosslinks provided by the metallophilic interactions is above or below its gel point.

16. The hybrid crosslinked dynamic polymer of claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and benzene-fluorobenzene interactions in the crosslinked network, wherein the degree of covalent crosslinks is above the gel point and the degree of supramolecular interactions crosslinks provided by the benzene-fluorobenzene interactions is above or below the gel point.

17. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and ionic hydrogen bonding, wherein the degree of covalent crosslinks is above its gel point and the degree of supramolecular crosslinking provided by ionic hydrogen bonding is above or below its gel point.

18. The hybrid crosslinked dynamic polymer of claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and halogen bonds in the crosslinked network, and the degree of crosslinking of the supramolecular interaction provided by the halogen bonds is above or below its gel point.

19. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and cation-pi interactions in the crosslinked network, the cation-pi interactions providing supramolecular interactions crosslinking with a degree of crosslinking above or below its gel point.

20. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and anionic-pi interactions in the crosslinked network, the degree of crosslinking of the supramolecular interactions provided by the cationic-pi interactions being above or below its gel point.

21. The hybrid crosslinked dynamic polymer according to claim 1, wherein the hybrid crosslinked dynamic polymer comprises only one crosslinked network and contains both covalent crosslinks and free radical cationic dimerization, the degree of crosslinking of the supramolecular crosslinks provided by the free radical cationic dimerization being above or below its gel point.

22. The hybrid crosslinked dynamic polymer according to claim 1, wherein the formulation components constituting the dynamic polymer further comprise any one or more of the following additives: other polymers, auxiliaries, fillers;

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

23. The hybrid crosslinked dynamic polymer according to any of claims 1 to 22, wherein the dynamic polymer or its composition form has any of the following: gel, ordinary solid, elastomer, foam.

24. The hybrid cross-linked dynamic polymer according to any one of claims 1 to 22, which is applied to self-healing materials, sealing materials, tough materials, adhesives, toy materials, stationery materials, shape memory materials, force sensor materials, energy storage device materials.