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

A kind of hybrid cross-linked dynamic aggregation object

Technical field:

The present invention relates to intelligent polymer fields, and in particular to a kind of hydridization friendship being made of covalent bond and supermolecular mechanism Link state polymer.

Background technique:

Hybrid cross-linked network structure (such as inierpeneirating network structure) is a kind of structure that can effectively improve polymer performance, In covalent inierpeneirating network structure, in order to obtain enough toughness, generally require to carry out first network big swelling (such as It is swollen with solvent or the second network), it is obtained when in use with sacrificing first network (the irreversible fracture of covalent bond) Irreversible toughness.The dynamic aggregation object of this kind of covalently hybrid cross-linked network not can be carried out any reparation not only after disruption, Lack dynamic, cannot effectively reuse, is very restricted its performance and application.

Supermolecular mechanism is a kind of noncovalent interaction emerging in recent years, being capable of shape again after active force dissociation At realizing the selfreparing effect of polymer.There is article report to be prepared into based on various supermolecular mechanisms in recent years dynamic The dynamic aggregation object of state polymer, non-covalent makes some progress in recent years.But many reports are individually Dynamic aggregation object is prepared using supermolecular mechanism, without the support of covalent cross-linking network, obtained dynamic aggregation object is general All there is poor mechanical property, which greatly limits the application ranges of dynamic aggregation object.

Therefore, it is necessary to develop a kind of novel hybrid cross-linked dynamic aggregation object, so that system can either have dimensionally stable Property, and have good mechanical property and excellent dynamic, to solve problems of the prior art.

Summary of the invention

For above-mentioned background, the present invention provides the present invention relates to a kind of hybrid cross-linked dynamic aggregation objects, which is characterized in that The hybrid cross-linked dynamic aggregation object, contains the covalent cross-linking formed by covalent bond and at least one parent's metal that is selected from is made With, halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, ion hydrogen bond action, radical cation two The supermolecular mechanism of poly- effect；Wherein, more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network.

In embodiments of the present invention, other supermolecules are also optionally contained in the hybrid cross-linked dynamic aggregation object Effect, wherein other supermolecular mechanisms include dipole-dipole effect, hydrogen bond action, metal-ligand effect.

In heretofore described hybrid cross-linked dynamic aggregation object, other supermolecular mechanisms can be non-crosslinked effect in chain And/or interchain linkage acts on and/or non-crosslinked effect.

A preferred embodiment (the first polymer network structure) according to the present invention, the hybrid cross-linked dynamic Polymer only contains a cross-linked network, and contains covalent cross-linking and supermolecular mechanism simultaneously in this cross-linked network, In, for the degree of cross linking of covalent cross-linking more than its gel point, the degree of cross linking of the crosslinking of supermolecule provided by supermolecular mechanism is solidifying at it Glue point above and below.

Another preferred embodiment (second polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and supermolecular mechanism and At least one other supermolecular mechanism, wherein the degree of cross linking of covalent cross-linking is more than its gel point, provided by supermolecular mechanism The degree of cross linking of supermolecule crosslinking in its gel point above and below, the crosslinking of supermolecular mechanism provided by other supermolecular mechanisms The degree of cross linking is in its gel point above and below.

Another preferred embodiment (the third polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and supermolecular mechanism simultaneously, wherein The degree of cross linking of covalent cross-linking reaches gel point or more, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is solidifying at it Glue point above and below；Another cross-linked network only contains at least one other supermolecular mechanism, wherein other supermolecules are made The degree of cross linking being crosslinked with provided supermolecule is more than its gel point.

Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network contains supermolecular mechanism, wherein supermolecular mechanism provided by supermolecular mechanism is handed over The degree of cross linking of connection is more than its gel point.

Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it It is more than glue point；Another cross-linked network contains supermolecular mechanism, wherein the crosslinking of supermolecular mechanism provided by supermolecular mechanism The degree of cross linking more than its gel point；Also contain at least one other supermolecular mechanism at least one cross-linked network simultaneously, Wherein, the degree of cross linking of the crosslinking of supermolecular mechanism provided by other supermolecular mechanisms is in its gel point above and below.

Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are three, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network only contains supermolecular mechanism, wherein supermolecular mechanism provided by supermolecular mechanism The degree of cross linking of crosslinking is more than its gel point；Third cross-linked network only contains at least one other supermolecular mechanism, wherein its The degree of cross linking of the crosslinking of supermolecular mechanism provided by its supermolecular mechanism is in its gel point above and below.

Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network contains supermolecular mechanism and covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it More than glue point, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.

Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it It is more than glue point；Another cross-linked network contains the degree of cross linking of supermolecular mechanism and covalent cross-linking and covalent cross-linking in its gel Or more, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below；Simultaneously Also contain at least one other supermolecular mechanism at least one cross-linked network, wherein provided by other supermolecular mechanisms The degree of cross linking of supermolecular mechanism crosslinking is in its gel point above and below.

Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention, the dynamic aggregation object contains There is at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein at least The noncrosslinking supermolecule polymer containing supermolecular mechanism is scattered in one network.

Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention, the dynamic aggregation object contains There is at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein at least The noncrosslinking supermolecule polymer containing supermolecular mechanism and at least one other supermolecular mechanism is scattered in one network.

Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention, the dynamic aggregation object Containing at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein extremely The existing cross-linked polymer containing supermolecular mechanism in granular form is scattered in a few network.

Another preferred embodiment (the 12nd kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein extremely The existing friendship containing supermolecular mechanism and at least one other supermolecular mechanism in granular form is scattered in a few network Linked polymer.

Another preferred embodiment (the 13rd kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and close metal in this cross-linked network With, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the crosslinking of the crosslinking of supermolecular mechanism provided by close metal function Degree is in its gel point above and below.

Another preferred embodiment (the 14th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and benzene-fluorobenzene in this cross-linked network With, wherein for the degree of cross linking of covalent cross-linking more than its gel point, benzene-fluorobenzene acts on the friendship of provided supermolecular mechanism crosslinking Connection degree is in its gel point above and below.

Another preferred embodiment (the 15th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and ion hydrogen bond in this cross-linked network With, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the friendship of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action Connection degree is in its gel point above and below.

Another preferred embodiment (the 16th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and contains covalent cross-linking and halogen bond effect simultaneously in this cross-linked network, The degree of cross linking of the crosslinking of supermolecular mechanism provided by halogen bond effect is in its gel point above and below.

Another preferred embodiment (the 17th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and cation-π in this cross-linked network With cation-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.

Another preferred embodiment (the 18th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and anion-π in this cross-linked network With cation-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.

Another preferred embodiment (the 19th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and free radical sun from Sub- dimerization, the degree of cross linking of the crosslinking of supermolecular mechanism provided by radical cation dimerization more than its gel point or Below.

In embodiments of the present invention, the close metal function refers to that when two outermost electron structures be d¹⁰ Or d⁸Generate interaction force when metal ion is close to less than the sum of its van der Waals radius, form close metal function.

In embodiments of the present invention, the halogen bond effect is referred to by halogen atom or lewis acid and neutrality Or the noncovalent interaction formed between electronegative lewis base.

In embodiments of the present invention, cation-π effect is referred to by the π of cation and armaticity system The noncovalent interaction formed between electron system.

In embodiments of the present invention, anion-π effect, refers to by anion and electron-deficient aromatic π body The noncovalent interaction formed between system.

In embodiments of the present invention, the benzene-fluorobenzene effect, refers to by leading between aromatic hydrocarbons and more fluorinated aromatic hydrocarbons It crosses dispersion force and quadrupole moment acts on the noncovalent interaction collectively constituted.

In embodiments of the present invention, the ion hydrogen bond action, by the radical cation that can form hydrogen bond action Group and anion group are constituted, the coulomb interaction being formed simultaneously between hydrogen bond action and negative ions, or by that can form hydrogen bond action Positive/negative ionic group and neutral hydrogen bond group constitute, be formed simultaneously between hydrogen bond action and positive/negative ion and neutral group from Son-dipole effect.

In embodiments of the present invention, the radical cation dimerization, construction unit are to contain simultaneously The group of free radical and cation.

In embodiments of the present invention, dipole-dipole effect refers to the atom different when two kinds of electronegativity When bonding, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, produces Eelctric dipole is given birth to, is interacted between two eelctric dipoles, dipole-dipole effect is formed.

In embodiments of the present invention, the hydrogen bond action, by being present in dynamic aggregation object chain backbone (including side Chain/branch/bifurcated chain), side group, appoint in end group and to form hydrogen bond between one or more hydrogen bond group and constitute.The hydrogen Key group preferably comprises following constituent:

At least one of further preferably following constituent:

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.

In embodiments of the present invention, metal-ligand effect, the ligand groups (being indicated with L) are selected from ring Pentadiene and the structural unit for containing at least one coordination atom (indicating with A).One coordination atom can with one or Multiple metal centers (include but are not limited to metal ion, the metal center of metallo-chelate, metal-organic metal Metal center in center, metal inorganic compound, is indicated with M) one or more coordinate bonds are formed, a metal center can also To form one or more coordinate bond with one or more coordination atom.One ligand groups is matched with what metal center was formed The quantity of position key is known as the numbers of teeth of ligand groups, and in embodiments of the present invention, in the same system, metal center can be with One of one tooth ligand, bidentate ligand, tridentate ligand or multiple ligands form metal-ligand effect, go back between different ligands Cyclization may be connected by metal center, therefore the present invention can effectively provide type, quantity and performance dynamic abundant enough Property metal-ligand effect, structure shown in the following general formula is some to provide example, but the present invention is not limited only to this:

Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, including but not only limit In boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It needs to illustrate , A exists in the form of anion sometimes；It is cyclopentadiene ligand.In the present invention, it is preferred to which a coordination atom is only A coordinate bond is formed with a metal center, therefore the quantity of the coordination atom contained in ligand groups is ligand groups The number of teeth.The metal-ligand that the ligand groups and metal center are formed acts on (with M-L_xIt indicates, in x expression and the same metal The quantity of the ligand groups of heart phase separation) power and the type and quantity of coordination atom in ligand groups, metal center Type and valence state and ion pair etc. are related.

The metal center M can be the metal center of any appropriate metal ion or compound/chelate etc., It can be selected from any appropriate ionic species of any one metal, compound/chelate and combinations thereof in the periodic table of elements.

In embodiments of the present invention, the form of the dynamic aggregation object can be ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), foamed material Deng.

In embodiments of the present invention, a kind of dynamic aggregation object containing combination supermolecular mechanism, constitutes dynamic aggregation The raw material components of object further include it is following any or appoint it is several can additive: other polymers, auxiliary agent, filler；

Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis tree Rouge, synthetic rubber, synthetic fibers；

Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light are stablized Agent, heat stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, Dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；

Wherein, addible filler be selected from it is following any or appoint several fillers: inorganic non-metallic filler, metal packing, Organic filler.

The hybrid cross-linked dynamic aggregation object in embodiments of the present invention is applied to following product: selfreparing Property material, sealing material, toughness material, adhesive, toy material, stationery material and shape memory material, force snesor material, Energy storage device material.

Compared with prior art, the invention has the following advantages:

(1) in dynamic aggregation object of the invention, covalent cross-linking and selected is existed simultaneously in a polymeric system Close metal function, halogen bond effect, cation-π effect, anion-π effect, the effect of π-π stacking, benzene-fluorobenzene effect, ionic hydrogen At least one of key effect, radical cation dimerization supermolecular mechanism.The generation type of selected supermolecular mechanism is abundant, There is stronger sensibility to external environment, by the regulation to external environment, can make dynamic based on these supermolecular mechanisms State polymer has more sensitive dynamic property, such as the directionality of halogen bond effect, cation-π effect, anion-π effect can Control selectivity and controllable identity, benzene-fluorobenzene effect order, the pH of ion hydrogen bond action, concentration sensitive, electric conductivity, The characteristics such as special photo electric of close metal interaction, radical cation dimerization, can according to demand reasonable selection it is super Molecular action group/unit carries out MOLECULE DESIGN.Stablize by force in addition, providing one by covalent cross-linking for dynamic aggregation object Network structure, polymer can keep balanced structure, realize " being association of activity and inertia " of supermolecular mechanism and covalent bond, polymerizeing It shows to act synergistically in object network, provides enough toughness for cross-linked polymer, so that cross-linked polymer is possessing crosslinking While the intrinsic mechanical strength of structure and stability, also possess excellent tensile toughness and tear resistance.

(2) also contain other optional supermolecular mechanisms in the present invention in dynamic aggregation object, make full use of and combine and is each The advantages of supermolecular mechanism, dipole-dipole act on temperature sensitive property, can be used to realize the preparation of temperature-responsive material, hydrogen The active force of key effect and metal-ligand effect is generally bigger, can be supplemented for the mechanical property of dynamic aggregation object, together When, intensity, structure, dynamic, responsiveness and formation condition of the supermolecular mechanism of different series etc. are different, can achieve The collaboration orthogonal impact of performance again, enable material obtain the self-repairability of orthogonality, plasticity, can re-workability.

(3) dynamic aggregation object dynamic action of the invention is abundant, effect is controllable.It can pH value by environment, solvent pole Property, temperature, light wave, the external conditions such as redox or electromagnetic field specific regulatory control is carried out to the dynamic of supermolecular mechanism, make The dynamic action of dynamic aggregation object is more abundant, prepares the dynamic aggregation object of different response performances, extends answering for polymer Use range.

With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.

Specific embodiment

The present invention relates to a kind of hybrid cross-linked dynamic aggregation objects, which is characterized in that the hybrid cross-linked dynamic aggregation object, It contains the covalent cross-linking formed by covalent bond and at least one selected from close metal function, halogen bond effect, cation-π effect, yin Ion-π effect, benzene-fluorobenzene effect, ion hydrogen bond action, radical cation dimerization supermolecular mechanism；Wherein, altogether It is more than the gel point that valence crosslinking reaches covalent cross-linking at least one cross-linked network.

Term " polymerization " reaction/action used refers to the reactant of lower molecular weight if not otherwise indicated in the present invention Propagation process/the effect with the product of higher molecular weight is formed by reaction formations such as polycondensation, addition polymerization, ring-opening polymerisations.Its In, reactant can be that (can spontaneously be polymerize with polymerizing power, or in initiator or can add outside and can act on It is lower to be polymerize) the compounds such as monomer, oligomer, prepolymer.It is referred to as equal by a kind of product that reactant is polymerize Polymers.Copolymer is known as by the product that two or more reactant is polymerize.Described in the present invention is " poly- Close " comprising linear growth process, branching process, annulation process and cross-linking process of reactant molecule chain etc.；In the present invention Embodiment in, " polymerization " includes propagation process caused by bonding and noncovalent interaction as covalent bond.

Term " crosslinking " reaction/action used in the present invention, if not otherwise indicated, refer between reactant molecule and/or The physical action of chemical bonds and supermolecular mechanism in reactant molecule between covalent bond, which is formed, has two dimension, three-dimensional cluster And/or the process of three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is general first to be carried out in two-dimensional/three-dimensional direction Increase, gradually form two dimension or three-dimensional cluster, developing deeply is three-dimensional infinite network structure.It should be noted that in the present invention Cross-linked structure, refers in particular to the three-dimensional infinite network structure of gel point or more (containing gel point, similarly hereinafter), and what non-crosslinking structure then referred to It is the structures such as line style, ring-type, branching and gel point two dimension below, three-dimensional cluster structure.Heretofore described " gel Point " (also referred to as percolation threshold), refers to reactant in cross-linking process, and viscosity is uprushed, and starts gel phenomenon occur, for the first time Start reflecting point when crosslinking reaches a three-dimensional infinite network.When there are a variety of crosslinked actions, except covalent cross-linking is at least It is outer to reach its gel point or more in one network, other crosslinked actions can be in its gel point above and below.

In embodiments of the present invention, covalent cross-linking can have one or more than one kinds of, also can be using any Suitable covalent cross-linking chemical structure, topological structure, degree of cross linking and combinations thereof.In embodiments of the present invention, cross-linked network There can be at least one, namely can be single one network, there can also be the multiple networks being mutually blended, there can also be interpenetrating Multiple networks.But in embodiments of the present invention, the covalent cross-linking must reach covalent at least one network It is more than the gel point of crosslinking.In this way, for polymer of the invention, can just guarantee even if in only one network the case where Under, polymer can also keep balanced structure, namely can be the insoluble structure not melted in the normal state.It is handed over except covalent It networks outside network, can also be containing other crosslinkings or noncrosslinking ingredient, including singly it is not limited only to polymer, small molecule, inorganic Material composition；Wherein the topological structure of component of polymer may include but be not limited only to line style, branching, ring-type, cluster, crosslinking.

In embodiments of the present invention, supermolecular mechanism by any suitable location in dynamic aggregation object includes but not only It is limited to polymer backbone, side group, the supermolecular mechanism group in end group/unit interaction and realizes.And any position Supermolecular mechanism in chain can be formed between supermolecular mechanism group under certain condition, supermolecular mechanism is not direct in such chain Crosslinked action is generated, but if generating nested rings can then cause to be crosslinked.In addition, in the present invention under normal conditions, by bone Polymer can be caused to form microphase-separated, skeleton oversubscription under the supermolecular mechanism certain condition that frame supermolecular mechanism group provides Son effect is present in hard phase and constitutes strong non-covalent together with hard phase, on the one hand play increase balanced structure stability and On the other hand the effect of mechanical strength promotes toughness based on its non-covalent character.In the present invention, same polymer chain/molecule/ May exist one or more than one identical or different supermolecular mechanism in network, the supermolecule in any one network is made With can be in any crosslinking degree.

In embodiments of the present invention, the skeleton supermolecular mechanism group/unit, refers in the group/unit At least one atom directly participate in the continuous main polymer chain of building or main polymer chain or crosslinking on cross-linked network skeleton Link；The side group supermolecular mechanism group/unit, refers to all atoms on the group/unit in side group；It is described End group supermolecular mechanism group/unit, refer to all atoms on the group/unit on end group.The skeleton oversubscription Son effect group/unit can be to be generated in polymer polymerizing/cross-linking process, namely by forming the supermolecular mechanism base Group/unit and generate polymerized/cross-linked；It is also possible to pre-generate and carries out polymerized/cross-linked again；It is preferred that pre-generated.The side group Supermolecular mechanism group/unit can before polymerized/cross-linked, later or in the process generate, before or after the number that generates Amount can be than relatively freely controlling.

In the present invention, " main polymer chain " refers to having most in polymer architecture if not otherwise indicated The chain of multichain joint number." side chain " refers in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone The molecular weight for being connected and being distributed in its skeleton side is more than the chain structure of 1000Da；Wherein, the branch, bifurcated chain refer to It is the link that the molecular weight come out from main polymer chain skeleton/cross-linked network chain backbone or any other chain bifurcated is more than 1000Da Structure；For the sake of simplicity, the molecular weight of side chain, branch, bifurcated chain if not otherwise indicated, is then collectively referred to as side when being more than 1000Da Chain." side group ", refer to being connected in polymer architecture with main polymer chain skeleton/cross-linked network main chain backbone and Chemical group of the molecular weight not higher than 1000Da and molecular weight that are distributed in main chain backbone side are not higher than the short-side chain of 1000Da. For side chain and side group, can have multilevel structure namely side chain that can continue with side group and side chain, the side chain of side chain can be with Continue have side group and side chain, side chain therein also includes branch and bifurcated chain isodesmic structure." end group " is referred to poly- Close the chemical group for being connected and being located at chain backbone end in object structure with polymer chain skeleton；In the present invention, under specific condition Side group can also have end group.

A preferred embodiment (the first polymer network structure) according to the present invention, the hybrid cross-linked dynamic Polymer only contains a cross-linked network, and contains covalent cross-linking and supermolecular mechanism simultaneously in this cross-linked network, In, for the degree of cross linking of covalent cross-linking more than its gel point, the degree of cross linking of the crosslinking of supermolecule provided by supermolecular mechanism is solidifying at it Glue point above and below.For the embodiment, only contain a cross-linked network, the covalent cross-linking in system is flat for providing Weigh structure, realizes dynamic effect by the dynamic of supermolecular mechanism；And it is upper more convenient in preparation.

Another preferred embodiment (second polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and supermolecular mechanism and At least one other supermolecular mechanism, wherein the degree of cross linking of covalent cross-linking is more than its gel point, provided by supermolecular mechanism The degree of cross linking of supermolecule crosslinking in its gel point above and below, the crosslinking of supermolecular mechanism provided by other supermolecular mechanisms The degree of cross linking is in its gel point above and below.In this embodiment, other super by being introduced in single cross-linked network structure Molecular action makes it possible to a supplement as supermolecular mechanism, so that polymer reflects moving with hierarchy State is reversible and quadrature-synergy effect.

Another preferred embodiment (the third polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and supermolecular mechanism simultaneously, wherein The degree of cross linking of covalent cross-linking reaches gel point or more, and the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is solidifying at it Glue point above and below；Another cross-linked network only contains at least one other supermolecular mechanism, wherein other supermolecules are made The degree of cross linking being crosslinked with provided supermolecule is more than its gel point.In this embodiment, independent by additionally introducing Other supermolecular mechanism cross-linked networks make it possible to a supplement as supermolecular mechanism dynamic, so that polymer can Embody the dynamic reversible effect with hierarchy.

Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network contains supermolecular mechanism, wherein supermolecular mechanism provided by supermolecular mechanism is handed over The degree of cross linking of connection is more than its gel point.In this embodiment, covalent cross-linking network is responsible for keeping balanced structure, is based on oversubscription The network of son effect is responsible for providing dynamic property, and covalent cross-linking network and supermolecular mechanism network can form interpenetrating or Semi-IPN Network the advantages of both making full use of, reaches collaboration and/or orthogonal dynamic effect.

Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it It is more than glue point；Another cross-linked network contains supermolecular mechanism, wherein the crosslinking of supermolecular mechanism provided by supermolecular mechanism The degree of cross linking more than its gel point；Also contain at least one other supermolecular mechanism at least one cross-linked network simultaneously, Wherein, the degree of cross linking of the crosslinking of supermolecular mechanism provided by other supermolecular mechanisms is in its gel point above and below.In the reality It applies in mode, supermolecular mechanism network and covalent cross-linking network be not directly in the same network, and the other oversubscription introduced Son effect can also make the dynamic ability of regulation and control of polymer stronger, and synergy is more preferable.

Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are three, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network only contains supermolecular mechanism, wherein supermolecular mechanism provided by supermolecular mechanism The degree of cross linking of crosslinking is more than its gel point；Third cross-linked network only contains at least one other supermolecular mechanism, wherein its The degree of cross linking of the crosslinking of supermolecular mechanism provided by its supermolecular mechanism is in its gel point above and below.Preferably In, supermolecular mechanism cross-linked network, other supermolecular mechanism cross-linked networks, covalent cross-linking network are respectively individually present, thus sharp Dynamic aggregation object is made to reveal different orthogonalities and collaboration from the difference of stability with dynamic between different cross-linked networks Property, reach better selfreparing effect.

Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is at it It is more than gel point；Another cross-linked network contains supermolecular mechanism and covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it More than glue point, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.? In the embodiment, by controlling the structure of two covalent cross-linking networks, Reasonable Regulation And Control dynamic aggregation object balance knot can achieve The purpose of structure and mechanical property.

Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention, described is hybrid cross-linked dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and the degree of cross linking of covalent cross-linking is solidifying at it It is more than glue point；Another cross-linked network contains the degree of cross linking of supermolecular mechanism and covalent cross-linking and covalent cross-linking in its gel Or more, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below；Simultaneously Also contain at least one other supermolecular mechanism at least one cross-linked network, wherein provided by other supermolecular mechanisms The degree of cross linking of supermolecular mechanism crosslinking is in its gel point above and below.In this embodiment, it is covalently handed over by control two Network the structure of network, can achieve the purpose of Reasonable Regulation And Control dynamic aggregation object balanced structure and mechanical property, and introduce its Its supermolecular mechanism can also make the dynamic ability of regulation and control of polymer stronger, and collaboration and selfreparing effect are more preferable.

Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention, the dynamic aggregation object contains There is at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein at least The noncrosslinking supermolecule polymer containing supermolecular mechanism is scattered in one network.The non-friendship containing supermolecular mechanism Join supermolecule polymer when by external force, supermolecular mechanism can arrive the effect for playing dynamic reversible, improve the resistance to of material Use performance.

Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention, the dynamic aggregation object contains There is at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein at least The noncrosslinking supermolecule polymer containing supermolecular mechanism and at least one other supermolecular mechanism is scattered in one network. The non-crosslinked supermolecule polymer containing supermolecular mechanism and at least one other supermolecular mechanism is by external force When, supermolecular mechanism can arrive the effect for playing dynamic reversible, improve durability, and the other supermolecular mechanisms introduced also can So that the dynamic ability of regulation and control of polymer is stronger, collaboration and selfreparing effect are more preferable.

Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention, the dynamic aggregation object Containing at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein extremely The existing cross-linked polymer containing supermolecular mechanism in granular form is scattered in a few network.It is described existing for particle For cross-linked polymer containing supermolecular mechanism when by external force, supermolecular mechanism can arrive the effect for playing dynamic reversible, Improve the durability of material.

Another preferred embodiment (the 12nd kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing at least one cross-linked network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and wherein extremely The existing friendship containing supermolecular mechanism and at least one other supermolecular mechanism in granular form is scattered in a few network Linked polymer.The cross-linked polymer with containing supermolecular mechanism and at least one other supermolecular mechanism existing for particle exists When by external force, supermolecular mechanism can arrive the effect for playing dynamic reversible, improve durability, and introduce other super Molecular action can also make the dynamic ability of regulation and control of polymer stronger, and collaboration and selfreparing effect are more preferable.

Another preferred embodiment (the 13rd kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and close metal in this cross-linked network With, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the crosslinking of the crosslinking of supermolecular mechanism provided by close metal function Degree is in its gel point above and below.In this embodiment, close metal function can be stabilized in the polymer, and effect is strong Spend it is moderate, and have certain directionality, do not have apparent saturability, can assemble and form polynuclear complex, by external environment Influence it is smaller, the dynamic of prepared polymer can be made more sufficient.

Another preferred embodiment (the 14th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and benzene-fluorobenzene in this cross-linked network With, wherein for the degree of cross linking of covalent cross-linking more than its gel point, benzene-fluorobenzene acts on the friendship of provided supermolecular mechanism crosslinking Connection degree is in its gel point above and below.It in this embodiment, can using benzene-fluorobenzene effect invertibity and sedimentation To prepare the dynamic aggregation object with specific function.

Another preferred embodiment (the 15th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and ion hydrogen bond in this cross-linked network With, wherein the degree of cross linking of covalent cross-linking is more than its gel point, the friendship of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action Connection degree is in its gel point above and below.In this embodiment, ion hydrogen bond has very strong sensibility to pH, passes through control PH value in system can be realized the adjusting to dynamic aggregation object dynamic.

Another preferred embodiment (the 16th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and contains covalent cross-linking and halogen bond effect simultaneously in this cross-linked network, The degree of cross linking of the crosslinking of supermolecular mechanism provided by halogen bond effect is in its gel point above and below.In this embodiment, halogen The many kinds of and various structures of key can be to the structure of dynamic aggregation object by the design effectively to halogen key donor and receptor It is effectively adjusted with dynamic, is based on halogen bond effect, can be designed that the dynamic aggregation object of order, self-repairability.

Another preferred embodiment (the 17th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and cation-π in this cross-linked network With cation-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.In the embodiment party In formula, the type of cation-π effect is abundant, and moderate strength can steadily be present in various environment, is based on cation-π Effect can prepare performance dynamic aggregation object abundant.

Another preferred embodiment (the 18th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and makees simultaneously containing covalent cross-linking and anion-π in this cross-linked network With cation-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.In the embodiment party In formula, anion-π effect has invertibity and controllable identity, and the dynamic aggregation with property can be constructed with it Object.

Another preferred embodiment (the 19th kind of polymer network structure) according to the present invention, described is hybrid cross-linked Dynamic aggregation object only contains a cross-linked network, and in this cross-linked network simultaneously containing covalent cross-linking and free radical sun from Sub- dimerization, the degree of cross linking of the crosslinking of supermolecular mechanism provided by radical cation dimerization more than its gel point or Below.In this embodiment, can be prepared using photoelectric characteristic possessed by radical cation dimerization has spy Different functional dynamic aggregation object.

The present invention can also have other diversified hybridization network structural implementations, can contain in an embodiment There are three or above identical or different network, those skilled in the art can be closed with logic according to the present invention and train of thought Reason effectively realizes.

In embodiments of the present invention, the close metal function refers to that when two outermost electron structures be d¹⁰ Or d⁸Generate interaction force, two metals of close metal function when metal ion is close to less than the sum of its van der Waals radius Ion can be the same or different.The outermost electron structure is d¹⁰Metal ion include but are not limited to Cu⁺、Ag⁺、Au⁺、 Zn²⁺、Hg²⁺、Cd²⁺, preferably Au⁺、Cd²⁺；The outermost electron structure is d⁸Metal ion include but not only limit In Co⁺、Ir⁺、Rh⁺、Ni²⁺、Pt²⁺、Pb²⁺, preferably Pt²⁺、Pb²⁺.Close metal function can be stabilized in the polymer, effect Moderate strength, and there is certain directionality, do not have apparent saturability, can assemble and form polynuclear complex, by extraneous ring The influence in border is smaller, and the dynamic of prepared polymer can be made more sufficient.

In embodiments of the present invention, forming the combination of close metal function, there is no particular restriction, if metal ion it Between form suitable close metal function.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

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 embodiments of the present invention, the halogen bond effect, refer to by halogen atom with it is neutral or negatively charged Lewis base between the noncovalent interaction that is formed, essence be halogen atom σ antibonding orbital with there is lone electron pair Interaction between atom or pi-electron system.The interaction of halogen key can use-XY-expression, 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.Halogen key has directionality, tendency In linear geometrical characteristic；With the increase of halogen atom ordinal number, combinative electron donor number can also increase, formation Halogen bond strength is also higher.Based on halogen bond effect, the dynamic aggregation object of order, self-repairability can be designed that.

In embodiments of the present invention, there is no restriction for the formation atom combination of halogen bond effect, as long as can be in dynamic aggregation Stable halogen bond effect is formed in object.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

—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 embodiments of the present invention, cation-π effect is referred to by the π of cation and armaticity system The noncovalent interaction formed between electron system.Cation-π effect mainly has three categories, and the first kind is simple inorganic sun Ion or ion cluster (such as Na⁺、K⁺、Mg²⁺、NH₄ ⁺、Ca²⁺) and aroma system between effect；Second class be organic cation (such as Quaternary ammonium cation) and aroma system between effect；Third class is atom positively charged in the dipolar bond (H in such as N-H key Atom) and aroma system between effect.The type of cation-π effect is abundant, moderate strength, can steadily be present in each In kind environment, performance dynamic aggregation object abundant can be prepared based on cation-π effect.

In embodiments of the present invention, the type of cation-π effect is not particularly limited, as long as long as can be Stable cation-π effect is formed in dynamic aggregation object.Some suitable cation groups can be exemplified below, but this Invention is not limited only to this:

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

In embodiments of the present invention, anion-π effect, refers to by anion and electron-deficient aromatic π body The noncovalent interaction formed between system.The anion can be simple inorganic non-metallic ion or ion cluster (such as Cl^-、Br^-、 I^-、OH^-)；It is also possible to organic anionic groups (such as benzene sulfonic acid base)；It can also be negatively charged in dipolar bond Atom (chlorine atom in such as C-Cl key).The electron-deficient aromatic π system refers to the difference due to ring member nitrogen atoms electronegativity, ring Pi-electron cloud Density Distribution and uneven, pi-electron is mainly to the high atomic orientation offset of electronegativity, so as to cause the π electricity of aromatic rings Sub- cloud distribution density decline, such as pyridine, fluorobenzene.Anion-π effect has invertibity and controllable identity, can use its structure Build the dynamic aggregation object for providing the energy that has specific characteristics.

In embodiments of the present invention, the type of anion-π effect is not particularly limited, as long as long as can be Stable anion-π effect is formed in dynamic aggregation object.Some suitable anion can be exemplified below, but the present invention It is not limited only to this:

Cl^-、Br^-、I^-、OH^-、SCN^-。

Some suitable electron-deficient aromatic π systems can be exemplified below, but the present invention is not limited only to this: pyridine, pyridazine, fluorine Benzene, nitrobenzene, four oxa- cup [2] aromatic hydrocarbons [2] triazines, three acid imide of benzene.

In embodiments of the present invention, the benzene-fluorobenzene effect, refers to by leading between aromatic hydrocarbons and more fluorinated aromatic hydrocarbons It crosses dispersion force and quadrupole moment acts on the noncovalent interaction collectively constituted.Since the ionization potential of fluorine atom is very high and atom polarization Rate and atomic radius are all smaller, in more fluorinated aromatic hydrocarbons the fluorine atom of surrounding because electronegativity it is big and negatively charged, center carbocyclic skeleton Electronegativity is smaller and has positive charge.Because the electronegativity of carbon atom be greater than hydrogen atom, the electric direction of aromatic hydrocarbons with The electric of more fluorinated aromatic hydrocarbons is contrary, and due to the volume very little of fluorine atom, the volume phase of more fluorinated aromatic hydrocarbons and aromatic hydrocarbons Closely, thus aromatic hydrocarbons and more fluorinated aromatic hydrocarbons by it is alternate face-to-face in a manner of sedimentation, form column packed structures, and this accumulation Mode is not influenced substantially by functional group is introduced.Using benzene-fluorobenzene effect invertibity and sedimentation, can prepare has The dynamic aggregation object of specific function.

In embodiments of the present invention, benzene-fluorobenzene effect type is not restricted, as long as can be in dynamic aggregation object Form stable benzene-fluorobenzene effect.Some suitable benzene-fluorobenzene effect can be exemplified below, but the present invention is not limited only to This:

In embodiments of the present invention, the combination of some suitable ion hydrogen bond actions can be exemplified below, but this hair It is bright to be not limited only to this:

In embodiments of the present invention, the radical cation dimerization, construction unit are to contain simultaneously The group of free radical and cation.As an example, it is described formed radical cation dimerization include but is not limited to It is lower to be lifted:

In embodiments of the present invention, the combination of some suitable radical cation dimerizations can illustrate such as Under, but the present invention is not limited only to this:

In embodiments of the present invention, dipole-dipole effect refers to the atom different when two kinds of electronegativity When bonding, since electronegativity makes distribution of charges uneven compared with the inducing action of thick atom, lead to the mal-distribution of electronics, produces Eelctric dipole is given birth to, is interacted between two eelctric dipoles, dipole-dipole effect is formed.Wherein, the eelctric dipole can be by any The different atomic bonding of suitable two kinds of electronegativity and generate, be exemplified below, but the present invention is not limited to this: 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, More preferable C ≡ N.Dipole-dipole effect can be stable be present in polymer, be easy to regulate and control, act on the pairing of group It can produce microdomai pi, make to interact more stable；When temperature is higher, dipole-dipole effect, which can weaken, even to disappear, therefore Polymer containing dipole-dipole effect can embody the difference of dynamic according to the difference of temperature.

In embodiments of the present invention, there is no particular restriction for the combination between dipole, as long as can be formed between dipole properly Dipole-dipole effect.Some suitable combinations can be exemplified below, but the present invention is not limited only to this:

In embodiments of the present invention, the hydrogen bond action is surpassed by any appropriate by what hydrogen bond was established Molecular action, the hydrogen atom being covalently attached to generally by the atom Z big with electronegativity and the atom that electronegativity is big, radius is small Y, using hydrogen as medium, generates the hydrogen bond link of Z-H ... Y shape formula, wherein described Z, the Y is any appropriate electricity between Z and Y Negativity is big and atom that radius is small, can may be not same element for same element, can be selected from F, N, O, C, S, Cl, P, the atoms such as Br, I, more preferably F, N, O atom, more preferably O, N atom.Wherein, the hydrogen bond action can be used as super Ring formation exists in molecule aggregation and/or crosslinking and/or chain namely hydrogen bond can be played only and connect two or more chains Segment unit, which plays to increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond, only plays the crosslinking of interchain supermolecule, Or only play in chain in combination of any two or more in ring formation or three of the above.The present invention is also not excluded for hydrogen Key plays the role of grafting.

In embodiments of the present invention, the hydrogen bond can be optional tooth number.Wherein, the number of teeth refer to by The donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group are formed by Hydrogen bond quantity, each H ... Y group are combined into a tooth.In following formula, the hydrogen of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bond groups Key bonding situation.

The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:

The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is with regard to weak, Ke Yiqi To the effect for promoting dynamic aggregation object to keep balanced structure and raising mechanical property (modulus and intensity).If the number of teeth of hydrogen bond Few, then intensity is low, and the dynamic of hydrogen bond action is with regard to strong.In embodiments of the present invention, the hydrogen bond of preferably more than four teeth is made With.

In embodiments of the present invention, the hydrogen bond action can be by existing between any appropriate hydrogen bond group Noncovalent interaction generates.Wherein, the hydrogen bond group can only contain hydrogen bond donor, or only contain hydrogen bond receptor, or Contain hydrogen bond donor and receptor simultaneously, preferably contains hydrogen bond donor and receptor simultaneously.Wherein, the hydrogen bond group preferably comprises Following constituent:

At least one of further preferably following constituent:

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.In embodiments of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, thio ammonia Carbamate base and the derivative of the above group etc..

In the present invention, the hydrogen bond group can be only present on polymer chain skeleton (including side chain/branch/point Fork chain), referred to as skeleton hydrogen bond group；Also it can be only present in polymer chain side group (also including the multilevel structure of side group), referred to as Side group hydrogen bond group；Also it can be only present on polymer chain/small molecule end group, referred to as end group hydrogen bond group；It can also be simultaneously On being present at least two in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group.When existing simultaneously In polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group at least two on when, under specific circumstances, Hydrogen bond can be formed between the hydrogen bond group of different location, such as skeleton hydrogen bond group can be formed between side group hydrogen bond group Hydrogen bond.

Wherein, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this):

Wherein, suitable side group hydrogen bond group/end group hydrogen bond group is in addition to it can have above-mentioned skeleton hydrogen bond group structure, More citings such as (but the present invention is not limited only to this):

Wherein, m, n are the quantity of repetitive unit, can be fixed value, are also possible to average value, preferably smaller than 20, more excellent Choosing is less than 5.

It in the present invention, can be same containing one or more kinds of hydrogen bond groups in same polymeric system It can also be a kind of or more containing that can contain in one or more kinds of hydrogen bond group namely dynamic aggregation object in cross-linked network The combination of kind hydrogen bond group.The hydrogen bond group can be formed by the reaction between any appropriate group, such as: it is logical The covalent reaction crossed between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups and amino is formed；It is logical Cross isocyanate groups and hydroxyl, sulfydryl, the covalent reaction between carboxyl are formed；Pass through succinimide group and amino, hydroxyl Covalent reaction between base, sulfydryl is formed.

In the present invention, the hydrogen bond action can be raw during dynamic aggregation object carries out the crosslinking of dynamic supermolecule At；Dynamic supermolecule crosslinking is carried out again after being also possible to pre-generated hydrogen bond action；It can also be cross-linked to form in dynamic supermolecule Afterwards, hydrogen bond action is generated during dynamic aggregation object subsequent forming, but the present invention is not limited only to this.

In the present invention, pass through the type and number of hydrogen bond group in control polymer chain skeleton and/or side group, Ke Yi Collocation and regulation are combined to the dynamic of polymer in a wide range of, the difference based on itself and various supermolecular mechanism dynamics It is different, the dynamic aggregation object that structure more horn of plenty, performance are more various, dynamic reversible effect has more hierarchy can be obtained.

In embodiments of the present invention, in order to form the crosslinking based on metal-ligand effect, a metal center is extremely It wants that metal-ligand effect (i.e. M-L can be formed with ligand groups described in two parts less₂Structure), there can also be multiple match Body and the same metal center form metal-ligand effect, and two of them or multiple ligand groups can be identical or different.One The ligancy of metal center is limited, and the coordination atom of ligand groups is more, and the amount of ligand that a metal center can be coordinated is got over It is few, it is lower based on metal-ligand effect supermolecule degree of cross linking；But each ligand is formed by the number of teeth with metal center and gets over More coordinations are stronger, and dynamic is lower, therefore the ligand groups of three teeth are preferably more than in the present invention.

In embodiments of the present invention, can only have one kind in a polymer chain or a dynamic polymer systems to match Body can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand refers to a kind of core ligand knot Structure, a framework counterpart, pendant ligands, end group ligand can have same core ligand structure, their difference exists The tie point and/or position difference of polymer chain or small molecule are accessed in core ligand structure.Suitable ligand combination can be with The dynamic aggregation object with particular characteristic is be effectivelyed prepared, such as plays collaboration and/or orthogonal effect, promotes the synthesis of material Performance.Suitable ligand groups (core ligand structure) can be exemplified below, but the present invention is not limited only to this:

One tooth ligand groups are exemplified below:

-C≡N；

Bidentate ligand group is exemplified below:

Tridentate ligand group is exemplified below:

Tetradentate ligands group is exemplified below:

Multidentate ligand is exemplified below:

In embodiments of the present invention, when there are the polymer of non-covalent or small molecules in dynamic polymer systems When compound, the core ligand structure can also be made in the polymer of the non-covalent or the end of small molecule compound For end group.

In embodiments of the present invention, the metal center M can be any appropriate metal ion or compound/ The metal center of chelate etc. can be selected from any appropriate ionic species, the chemical combination of any one metal in the periodic table of elements Object/chelate and combinations thereof.

Related metal is preferably the metal in the first subgroup to the 7th subgroup and the 8th race.First subgroup Metal into the 7th subgroup and the 8th race further include lanthanide series metal (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actinide metals (i.e. Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).

Related metal is more preferably the first subgroup (Cu, Ag, Au) metal, the second subgroup (Zn, Cd) metal, the 8th race (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) metal, group of the lanthanides (La, Eu, Tb, Ho, Tm, Lu) metal, actinium series (Th) metal.Into One step is preferably Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, to obtain stronger dynamic.

In embodiments of the present invention, there is no restriction for related metallo-organic compound, and suitable example can be lifted Under such as:

Other suitable metal organic compounds for being capable of providing metal center include but is not limited to the organic cage of metal-, metal- Organic frame.This metalloid-organic compound can be used alone, or is introduced by suitable covalent chemical on-link mode (OLM) The suitable position of polymer chain.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.

In embodiments of the present invention, the oxide of the preferably above-mentioned metal of related metal inorganic compound, vulcanization Composition granule, especially nano particle.

In embodiments of the present invention, the metallo-chelate that can provide suitable metal center preferably has coordination site empty Scarce chelate or some ligands can the chelate replaced the framework counterpart of the invention.

In embodiments of the present invention, there is no particular restriction for the combination of ligand groups and metal center, as long as matching physical efficiency Enough and metal center generates suitable metal-ligand and acts on.Some suitable combinations can be exemplified below, but the present invention is not It is only limitted to this:

In embodiments of the present invention, the generation or introducing of supermolecular mechanism group can use any appropriate reaction, Include but are not limited to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, and the parental materials of heterocycle are anti- It answers, the nucleophilic substitution of heterocycle, double bond radical reaction, the side chain reaction of heterocycle, nitrine-alkynes click-reaction, sulfydryl-is bis- Key/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester are reacted with amino； Preferred isocyanate and amino, hydroxyl, sulfydryl react, nitrine-alkynes click-reaction, the reaction of urea-amine, amidation process, Active ester is reacted with amino, sulfydryl-double bond/alkynes click-reaction；More preferable isocyanates and amino, hydroxyl, sulfydryl react, Sulfydryl-double bond/alkynes click-reaction, nitrine-alkynes click-reaction.

In embodiments of the present invention, the introducing of metal center can carry out on any suitable opportunity.At least one Lower three kinds of methods can introduce before generating ligand, can formerly with ligand formed metal-ligand effect composition again into Row polymerized/cross-linked can also be re-introduced into after completing polymerized/cross-linked.It is preferred that after generating ligand but before covalent cross-linking It introduces.

The generation type of supermolecular mechanism selected by the present invention is abundant, has stronger sensibility to external environment, by right The regulation of external environment can make the dynamic aggregation object based on these supermolecular mechanisms have more sensitive dynamic property, such as halogen The directionality of key effect, cation-π effect, the controllable selectivity of anion-π effect and controllable identity, benzene-fluorobenzene act on Order, the pH of ion hydrogen bond action, concentration sensitive, electric conductivity, dipole-dipole effect temperature sensitivity, close metal Interaction, radical cation dimerization the characteristics such as special photo electric, reasonable selection supermolecule can make according to demand MOLECULE DESIGN is carried out with group/unit.

Above-mentioned " covalent cross-linking ", process means can be any appropriate covalent cross-linking and means in principle.Refer generally to Then two ways, the prepolymer of first synthetic linear or branching type carry out interchain linkage reaction；Or from monomer, once Property or reaction reach crosslinking.

In embodiments of the present invention, the covalent cross-linking is established by any appropriate by covalent bond Covalent cross-linking link, includes but are not limited to the covalent cross-linking by carbon-carbon bond formation, the covalent friendship formed by carbon-sulfide linkage Connection, the covalent cross-linking formed by carbon-oxygen bond, the covalent cross-linking formed by carbon-nitrogen bond are formed covalent by silicon-oxygen key Crosslinking.Covalent cross-linking in any one cross-linked network structure of dynamic aggregation object can have at least one chemical structure, at least A kind of degree of branching and at least one reaction type and reaction means.

In embodiments of the present invention, covalent cross-linking can use any appropriate reaction, include but are not limited to following Type: by between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, epoxy group and hydroxyl Covalent reaction is crosslinked；Pass through carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, epoxy group Covalent reaction between amino is crosslinked；It is crosslinked by alkene radical reaction, free radical acrylate reaction；It is logical Cross the CuAAC reaction of azido group and alkynyl, the click-reaction progress covalent cross-linking of sulfydryl and alkene；By between silicone hydroxyl Condensation reaction carries out covalent cross-linking.

The relative molecular mass of term " molecular weight " used representative species in the present invention, for small molecule compound, small Molecular radical and certain macromolecular compounds with fixed structure, for macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And there is polydispersion for oligomer, high polymer, oligomer residue, high polymer residue etc. The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the small molecule compound in the present invention, small molecule Group refers in particular to the compound or group that molecular weight is no more than 1000Da；Macromolecular compound, that macro-radical refers in particular to molecular weight is big In the compound or group of 1000 Da.

Heretofore described " organic group " refers to the base mainly constituted using carbon and protium as skeleton Group can be the small molecule group that molecular weight is no more than 1000Da, be also possible to the polymer chain that molecular weight is greater than 1000Da Residue, suitable group are illustrated such as: methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde radical, acetyl group, acetonyl.

Term " hetero atom " used refers to nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom in the present invention Etc. common non-carbon.

Term " alkyl " used refers to the saturated hydrocarbyl with straight or branched structure in the present invention.In appropriate situation Under, alkyl can have specified carbon atom number, for example, C_1-4Alkyl, the alkyl be included in linear chain or branched chain arrangement in have 1, 2, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but is not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 4- methyl butyl, n-hexyl, 2- methyl amyl, 3- methylpent Base, 4- methyl amyl, 5- methyl amyl, 2- ethyl-butyl, 3- ethyl-butyl, heptyl, octyl, nonyl, decyl.

The single ring architecture being previously mentioned in the present invention is referred to containing only a ring in cyclic structure, be illustrated such as:

The multiring structure being previously mentioned refers to illustrating such as in cyclic structure containing two or more independent rings:

The spirane structure being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing one The cyclic structure of a atomic building is illustrated such as:

The condensed cyclic structure (it also includes two rings, virtue and ring structure) being previously mentioned, refers in cyclic structure containing by two A or multiple rings to each other by sharing the cyclic structure of two adjacent atomic buildings, citing such as:

The caged scaffold being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing two The cyclic structure of a above adjacent atomic building, has three-dimensional cage structure, illustrates such as:

The heterocycle structure being previously mentioned refers to participating in the cyclic annular knot to be formed containing at least one hetero atom in cyclic structure Structure is illustrated such as:

It, all can be in the case where not specifying when the structure being related in the present invention has isomer Any one of them isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..

In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " A or more than one hydrogen atom can be replaced any substituent group.In the case where being not particularly limited, substituent group therein It is not particularly limited.

For a compound, a group or an atom, can be substituted simultaneously and by hydridization, such as nitrobenzophenone Replace hydrogen atom, for another example-CH₂-CH₂-CH₂It is replaced by-CH₂-S-CH(CH₃)-。

In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention It may include the option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".

In embodiments of the present invention, the form of the dynamic aggregation object or its composition can be ordinary solid, water Gel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel, elastomer, foamed material Deng, wherein the dissolvable small-molecular-weight component content contained in ordinary solid and foamed material is generally not more than 10wt%, and coagulates The small-molecular-weight component content contained in glue is generally not less than 50wt%.The shape and volume of ordinary solid are relatively more fixed, have Better mechanical strength, can not be by the constraint of sweller.Elastomer have ordinary solid general properties, but have simultaneously compared with Good elasticity, and it is softer.Gel then has good flexibility, preferable resilience can be embodied, preferably by increasing Mould agent, oligomer, ionic liquid and boiling point it is higher than water organic solvent swelling gel.Foamed material then has density low, light Just the mechanical strength of the advantages of, the brittleness and gel that can also overcome the problems, such as part ordinary solid are relatively low, and soft foam material also has There is the characteristic of good elasticity and soft comfortable.The material of different shape can have suitable purposes in different fields.

In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.

In the preparation process of dynamic aggregation object, mechanical foaming method, physical blowing method, three kinds of chemical blowing process are mainly used Method foams to dynamic aggregation object.

Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be molded with as foamed material.To shorten, molding cycle can be passed through air and addition emulsifier or surface is living Property agent.

Wherein, the physical blowing method, be realized in the preparation process of dynamic aggregation object using physical principle it is poly- Close the foaming of object comprising but it is not limited only to following methods: (1) inert gas blown method, i.e., indifferent gas under pressurized condition Body is pressed into molten polymer or pasty material, then decompression heating, is made the gas expansion of dissolution and is foamed；(2) low boiling is utilized Point liquid evaporation gasification foaming makes liquid that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime It dissolves in polymer (particle), then heats and softens polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching, i.e., It is immersed in polymer with liquid medium and dissolves added solid matter in advance, make to occur a large amount of holes in polymer and be in hair Blister, such as by solable matter salt elder generation and mixed with polymers, put in water repeatedly after being shaped to product, then by product Processing dissolves out solable matter to get open-celled foam product is arrived；(4) hollow microsphere method is added hollow micro- in the material It is combined after ball as obturator-type foamed polymer；(5) expandable particles method is filled, first mixing filling expandable particles, Expandable particles are made to foam in molding or mixed process with the polymer material of activity foaming；Wherein, preferably by polymer In dissolve in inert gas and the method for low-boiling point liquid foams.Using physical blowing method, have operation Poisoning smaller, hair The advantages that bubble cost of material is lower, foaming agent noresidue body.Further, it is also possible to be prepared using freeze-drying.

Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam comprising but it is not limited only to following two method: (1) thermal decomposable foaming agent foaming utilizes chemistry The gas decomposed to give off after foaming agent heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, i.e., Using the chemical reaction occurred between two or more components in foaming system, inert gas (such as carbon dioxide or nitrogen are generated Gas) cause polymer to expand and foam.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to guarantee product There is preferable quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by polymerizeing The method for adding chemical foaming agent in object foams.

In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to form dynamic aggregation object foamed material.

Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material, which is direct plungeed into die cavity, carries out foaming；Two-step method, which refers to, first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam forms ratio Two-step method is easy to operate and high production efficiency, therefore it is preferred that one-step method carries out moulded from foam molding.

Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve Then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent in certain flow rate injecting material melt Under the action of form nuclei of bubbles.Expansion stage and solidifying and setting stage all occur after full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while so that foam is formed with the cooling of mold.

Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion process, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.

In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.

In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is then half open-celled structure that leading to again, which has mutual disconnected structure,.It, can also be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes: (1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be greater than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are greater than 0.4g/cm³, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm³, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm³, expansion ratio is greater than 9.

During the preparation process, certain addible other polymers, auxiliary agent, filler can also be added to be total in dynamic aggregation object With composition dynamic aggregation object material, but these additives it is not necessary to.

It is new can to play improvement material property, imparting material as additive in system for the other polymers Performance improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, it is optional From natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and possessed Molecular weight can be that oligomer or high polymer can according to the difference of polymeric species according to the difference of molecular weight without limitation Think homopolymer or copolymer, it in the specific use process should be according to the performance of target material and actual fabrication process It needs and is selected.

When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..

When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, Dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, Polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact poly Styrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetic acid second Enoate copolymer, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-second Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), poly- isoamyl two Alkene, poly- suitable butadiene, styrene-butadiene copolymer, hycar, polychlorobutadiene, isobutene-isoamyl Diene copolymers, polysiloxane, vinylidene-chlorotrifluoroethylene, epichlorohydrin ethylene oxide copoymer Deng.

In the preparation process of dynamic aggregation object material, the certain addible auxiliary agents being added can improve material Preparation process improves product quality and yield, reduces product cost or assign certain distinctive application performance of product.Described Addible auxiliary agent is selected from following any or several auxiliary agents: additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve helping for processing performance Agent, including lubricant, release agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersing agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent.

Catalyst in the addible auxiliary agent can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. Polyurethane catalyst for synthesizing: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), four Methyl dipropylenetriamine, N, N- dimethyl cyclohexyl amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl- N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as octanoic acid are sub- Tin, dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, ring Alkanoic acid cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；② Polyolefin catalyst for synthesizing: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalysis Agent, aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, Triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, aphthenic acids Rare earth etc.；3. CuAAC catalysts: sharing concerted catalysis by monovalence copper compound and amine ligand；Monovalence copper compound is optional From Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；Also selected from Cu (I) complex compound, such as [Cu (CH₃CN)₄]PF₆、 [Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] Amine (TBTA), three [(1- tert-butyl -1H-1,2,3- triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), it is hydrated bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts: photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, three Ethanol amine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used does not have It is particularly limited to, generally 0.01-0.5wt%.

Initiator in the addible auxiliary agent, can cause in polymerization process monomer molecule activate and Free radical is generated, reaction rate is improved, reaction is promoted to carry out, include but are not limited to following any or appoints several initiators: 1. radical polymerization shares initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), two carbon of peroxidating Sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate bis- (4- tert-butylcyclohexyl) esters, tert-butyl hydroperoxide Benzoic ether, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as Azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization With initiator: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system Deng；4. coordination polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；⑤ Ring-opening polymerisation initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, cause The preferred lauroyl peroxide of agent, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is without spy It does not limit, generally 0.1-1wt%.

Antioxidant in the addible auxiliary agent can delay the oxidation process of polymer material, guarantee material Successfully it can be processed and be prolonged its service life, include but are not limited to following any or appoint several antioxidant: by Hinder phenols, such as 2,6- di-tert-butyl-4-methy phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl benzene Phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert Butylphenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros equal three Piperazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '- Two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, it is such as thio Dipropionic acid dilauryl, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, phosphorous acid Three nonyl phenyl esters, three [2.4- di-tert-butyl-phenyl] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butylhydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyl] phosphorous Acid esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010).Institute Antioxidant dosage is not particularly limited, generally 0.01-1wt%.

Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers: photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultraviolet absorbing agent, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl； Pioneer's type ultraviolet absorbing agent, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-t-butyl -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer Agent, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvl base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- bis- tertiary fourths Base benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamate, N, the positive fourth positive group dithiocarbamates of N '-two Nickel formate etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.

Heat stabilizer in the addible auxiliary agent, enable to polymer material in processing or use process not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers: lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate Antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.

Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.

Lubricant in the addible auxiliary agent can be improved material lubricity, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid；Fatty acid ester, such as rouge Fat acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type, such as stearmide or tristearin Sour amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polyalcohols, it is such as stearic Alcohol, cetanol, pentaerythrite；Metal soap, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate. Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, lubricant quantity used is without spy It does not limit, generally 0.5-1wt%.

Release agent in the addible auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean, It includes but are not limited to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl Phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol etc.. Wherein, the preferred dimethicone of release agent, remover dosage used are not particularly limited, generally 0.5-2wt%.

Plasticizer in the addible auxiliary agent, can increase the plasticity of polymer material, so that polymer Hardness, modulus, softening temperature and brittle temperature decline, elongation at break, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Rouge Fat esters of gallic acid, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy glycerite Esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyl) oneself Ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetylated castor oil Sour methyl esters, dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, Trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP), plasticizer consumption used do not limit especially It is fixed, generally 5-20wt%.

Foaming agent in the addible auxiliary agent can make polymer samples foaming pore-forming, to obtain light, soft Soft or firm polymer material comprising but be not limited only to following any or appoint several foaming agents: physical blowing agent, such as third Alkane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether, chlorine Methane, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, Ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitro, N, N '-dimethyl-N, N '-dinitroso is to benzene two Formamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, azo two are different Butyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide,-two sulphur of biphenyl -4,4 ' Acyl azide；Physical microballoon/granule foaming agent, such as the expandable microballoon of Akzo Nobel company production；Foamed promoter, As urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, Zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, stearyl chloride, phthalyl chloride, maleic anhydride, benzene two Formic anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, ring Hexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, idol Nitrogen diformamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitro, N, N '-dimethyl-N, N '-two are sub- Nitro terephthalamide (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used are not particularly limited, and one As be 0.1-30wt%.

The deleterious charge assembled in polymer samples can be guided or be disappeared by the antistatic agent in the addible auxiliary agent It removes, it is made production and life not brought inconvenience or be endangered comprising but be not limited only to following any or appoint several antistatic Agent: anionic antistatic agent, as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, To nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, Fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, Dodecyl trimethylamine bromide；Amphoteric ion type antistatic agent, as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid of N- lauryl-N, N- Sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition Object, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, such as Polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, resist quiet The preferred lauryl trimethyl ammonium chloride of electric agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used It is not particularly limited, generally 0.3-3wt%.

Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid containing auxiliary agent Surface tension between phase is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any Kind appoints several emulsifiers: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid Sodium, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, Phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion Type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, as fatty alcohol polyoxyethylene ether, alkyl phenol are poly- Ethylene oxide ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythrite fat Acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecyl Benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used is without spy It does not limit, generally 1-5wt%.

Dispersing agent in the addible auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into carefully Small particle and be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms stable suspension comprising but be not limited only to following any or appoint several dispersing agents: yin Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as poly alkyl alcohol Ethylene oxide ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, it is such as bright Glue, water-soluble glue, lecithin, sodium alginate, lignosulfonates, polyvinyl alcohol etc..Wherein, the preferred detergent alkylate of dispersing agent Sodium sulfonate, naphthalene system methylene sulfonate (dispersing agent N), fatty alcohol polyoxyethylene ether, dispersant dosage used do not limit especially It is fixed, generally 0.3-0.8wt%.

Colorant in the addible auxiliary agent can make polymeric articles show required color, increase Surface color and polish comprising but be not limited only to it is following any or appoint several colorants: inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H₂G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc..Wherein, the selection of colorant does not need especially to limit depending on color sample demand Fixed, colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.

Fluorescent whitening agent in the addible auxiliary agent can make contaminated substance obtain the sparkling of similar fluorite Effect comprising but be not limited only to following any or appoint several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White dose of CBS), bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-hexichol second Alkenyl) double benzoxazoles (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002-0.03 wt%.

Delustering agent in the addible auxiliary agent when incident light being enabled to reach polymer surfaces, occurs unrestrained anti- It penetrates, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, the preferred titanium dioxide of delustering agent Silicon, delustering agent dosage used are not particularly limited, generally 2-5wt%.

Fire retardant in the addible auxiliary agent, can increase the flame resistance of material comprising but be not limited only to Under it is any or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, and one As be 1-20wt%.

Nucleating agent in the addible auxiliary agent can accelerate crystallization speed by the crystallization behavior of change polymer Rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, improves the product transparency, surface The purpose of the physical mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but Be not limited only to it is following any or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, the preferred dioxy of nucleating agent SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.

Rheological agent in the addible auxiliary agent can guarantee that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, can be improved its redispersibility comprising but not only limit In following any or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.

Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency is wrapped to meet various demands such as its stability and application performance in production, storage and use process It includes but is not limited only to following any or appoints several thickeners: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, fatty acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.

Levelling agent in the addible auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve and apply Film surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents: polyacrylate, Organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used are not particularly limited, generally 0.5-1.5wt%.

Antibacterial agent in the addible auxiliary agent, can within a certain period of time, make certain micro-organisms (bacterium, fungi, Saccharomycete, algae and virus etc.) growth or breeding be maintained at necessary below horizontal, be generally divided into inorganic antiseptic, You Jikang Microbial inoculum and natural antibacterial agent.Wherein, inorganic antiseptic include but are not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, Copper oxide, ammonium dihydrogen phosphate, lithium carbonate etc.；Organic antibacterial agent includes but are not limited to vanilla aldehydes, ethyl vanillin aldehydes, acyl group The organic compounds such as phenyl amines, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols；Natural antibacterial Agent includes but are not limited to chitin, mustard, castor oil, horseradish etc..Wherein, antibacterial agent preferably silver, zinc, vanilla aldehydes chemical combination Object, ethyl vanillin aldehydes compound, antibacterial agent dosage used are not particularly limited, generally 0.05-0.5wt%.

The addible filler, primarily serves following effect in the polymeric material: 1. reducing molded article Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical corrosion resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.

The addible filler, selected from following any or several fillers: inorganic non-metallic filler, metal are filled out Material, organic filler.

The addible inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, fullerene, two Molybdenum sulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, Flyash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass are micro- Pearl, foam microspheres, expandable particles, glass powder, cement, synthesis inorganic rubber, synthetic inorganic fiber, glass fibre, carbon fiber, Quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, whisker etc..

The addible metal packing, including metal simple-substance, metal alloy, metal oxide, metal inorganic chemical combination Object, metallo-organic compound etc. comprising but be not limited only to following any or appoint several: copper, silver, nickel, iron, gold etc. and its conjunction Powder, nano particle and the fiber of gold；Wherein, nano particle includes but are not limited to nanogold particle, nano-Ag particles, nanometer Palladium particle, nano cobalt granule, nano nickle granules, nano magnetic particle (such as γ-Fe₂O₃、CoFe₂O₄、NiFe₂O₄、MnFe₂O₄、 Fe₃O₄、FeN、Fe₂N、ε-Fe₃N、Fe₁₆N etc.)；It additionally include liquid metal comprising but it is not limited only to mercury, gallium, gallium indium liquid State alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Wherein, metallo-organic compound includes some ultraviolet The metallo-organic compound molecule or crystal that can be generated heat under line, infrared ray or electromagnetic action.

The addible organic filler includes but are not limited to following any or appoints several: fur, natural rubber Glue, synthesis organic rubber, synthetic organic fibre, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, Enzyme, hormone, raw lacquer, wood powder, shell powder, xylose, silk, artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..

Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, gold Belong to powder, natural rubber, protein, resin microbeads, amount of filler used is not particularly limited, generally 1-30wt%.

In the preparation process of dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, thermostabilization Agent, toughener, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of addible filler, barium sulfate, talcum powder, carbon black, glass Microballon, expandable particles, graphene, glass fibre, carbon fiber.

In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

The manufacturing method of composition of the invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Can blender etc. additive the subsequent operations such as be blended to prepolymer as needed, then be crosslinked, foamed.

The good dynamic characteristics that dynamic aggregation object elastomer of the invention is formed due to ion-dipole effect group/unit Supermolecular mechanism, dynamic aggregation object obtained simultaneously there are certain modulus, toughness, self-healing properties, can be wide The general elastic component etc. applied in adhesive, coating, film and structural composite material.

It is provided by the present invention a kind of with hybrid cross-linked dynamic aggregation object gel rubber material, preferably aqueous solution type gel material Material, organic solvent type gel rubber material and plasticizer swell gel material, more preferable plasticizer swell gel.

A kind of preparation method of dynamic aggregation object aqueous solution type gel rubber material of the invention, includes the following steps: for parent Aqueous monomers, by the raw material of hybrid cross-linked dynamic aggregation object (including the molecule containing ligand, metal center, chain extender, crosslinking agent And various auxiliary agents etc.) be added in aqueous solution, make prepared hybrid cross-linked dynamic aggregation object (reality according to the present invention Apply mode or be the dynamic aggregation object of single network or be interpenetrating networks dynamic aggregation object) mass fraction be 0.5 ~50%, covalent cross-linking is carried out by appropriate means, after reaction, a kind of dynamic aggregation object water-setting is made in natural cooling Glue, that is, one-step method prepare gel rubber material；The polymer chain network containing ligand can also be first prepared, makes it in aqueous solution Metal center is added after middle swelling, extra aqueous solution is removed after its gelation reaction.The aqueous solution is deionized water.

A kind of preparation method of dynamic aggregation object organic solvent type gel rubber material of the invention, include the following steps: for The raw material of hybrid cross-linked dynamic aggregation object is added in suitable organic solvent, makes prepared hydridization by the monomer of hydrophily difference The mass fraction for being crosslinked dynamic aggregation object is 0.5~50%, carries out covalent cross-linking by appropriate means, after reaction, natural It is cooling, that is, a kind of dynamic aggregation object organic solvent type gel rubber material is made, that is, one-step method prepares gel rubber material；It can also be first The polymer chain network containing ligand is prepared, metal center is added after being swollen it in suitable organic solution, it is solidifying to it It is taken out after gelatinization reaction and removes extra organic solvent.The organic solvent be acetone, butanone, N,N-dimethylformamide, One of chloroform, methylene chloride, dimethyl sulfoxide, tetrahydrofuran, methanol, dehydrated alcohol, ether, pentane and toluene Or it is a variety of.

A kind of dynamic aggregation object plasticizer swell gel material preparation method of the invention, includes the following steps: will have The raw material of hybrid cross-linked dynamic aggregation object is added in suitable plasticizer, makes the matter of prepared hybrid cross-linked dynamic aggregation object Measuring score is 0.5~50%, carries out covalent cross-linking by suitable method, after reaction, one kind is made in natural cooling Dynamic aggregation object is plasticized the gel of solvent swell, that is, one-step method prepares gel rubber material；It can also first prepare containing ligand Metal center is added after being swollen it in suitable plasticizer in polymer chain network, takes out and removes after its gelation reaction Extra plasticizer.Upper the plasticizer is selected from following any or appoints several: Phthalates: two fourth of phthalic acid Ester, dioctyl phthalate, diisooctyl phthalate, dibutyl phthalate (DHP), diisooctyl phthalate, neighbour Phthalic acid dinonyl, BBP(Butyl Benzyl Phthalate, butyl phthalate butyl glycolate, dicyclohexyl Bis- (13) esters of ester, phthalic acid, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Ring Oxygen compound class, as epoxy glycerite esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, The own ester of epoxystearic acid (2- ethyl), epoxy soybean oleic acid 2- ethylhexyl, two (2- second of 4,5- epoxy tetrahydrophthalic acid Base) own ester, Chinese littleleaf box methyl acetylricinolate, dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol； Class containing chlorine such as afforests paraffin class, chloro fat acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2- third Diol polyester；Phenyl alkylsulfonate, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, epoxy Change a kind of Environment-friendlyplastic plastic plasticizer of function admirable of soybean oil, epoxidation reaction system occurs for refined soybean oil and peroxide It is standby.It is resistance in polrvinyl chloride product to volatilize, is not easy to migrate, not easy to lose.This is to holding product light, thermal stability and extends use Service life is highly beneficial.Epoxidised soybean oil toxicity is minimum, is allowed for the packing timber of food and medicine by many countries Material is the epoxy plasticiser that uniquely can be used for packaging material for food of Food and Drug Adminstration of the US's approval.Of the invention In a kind of gel preparation of dynamic aggregation object plasticising solvent swell, the preferred epoxidized soybean oil of plasticizer.

In embodiments of the present invention, the oligomer is included but are not limited to: epoxy acrylate, modified epoxy third Olefin(e) acid ester, epoxy linseed oil triacrylate, polyester acrylic ester prepolymer, polyether acrylate, urethane acrylate Prepolymer, tripropylene glycol methoxy-ether mono acrylic ester, methoxy-ether neopentyl glycol propoxyl group mono acrylic ester, methoxy-ether three Hydroxymethyl-propane ethyoxyl diacrylate, the polymerization of amine modification acrylate, atoleine, number-average molecular weight less than 10000 Object；It is preferred that epoxy acrylate, polyester acrylate, polyether acrylate prepolymer, number-average molecular weight are poly- less than 10000 Urea, polycarbonate, polyester, polyethers or polyamide.

In embodiments of the present invention, the ionic liquid is included but are not limited to: glyoxaline ion liquid, pyridines Ionic liquid, quaternary ammonium ionic liquid, quaternary phosphine class ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid, alkenyl function Ionic liquid, Hydroxyl-functionalized Ionic Liquids, ether functionalized ion liquid, ester group functionalized ion liquid, carboxyl function can be changed Ionic liquid, itrile group functionalized ion liquid, amino functional ionic liquid, sulfonic acid funtionalized ionic liquid, benzyl function can be changed Ionic liquid, guanidine ionic liquid can be changed；It preferably specifically is selected from: 1- ethyl-3-methylimidazole tetrafluoroborate, 1- hexyl -2,3- Methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole bromide, N- octylpyridinium bromide, tributyhnethylammonium chloride, four Butyl bromide phosphine, N- butyl-N- crassitude bromide, N- butyl-N- methyl piperidine bromide, 1- vinyl -3- butyl imidazole Hexafluorophosphate, 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonate, 1- ethyl diethyldithiocarbamate ether -3- methylimidazole hexafluoro Phosphate, 1- ethyl acetate base -3- methylimidazole hexafluorophosphate, 1- carboxyethyl -3- methylimidazole bromide, 1- nitrile propyl -3- Methylimidazole hexafluorophosphate, 1- amine propyl -3- methylimidazole hexafluorophosphate, N- sulfonic acid butyl-pyridinium fluoroform sulphonate, 1- benzyl -3- methyl imidazolium tetrafluoroborate, tetramethylguanidine trifluoro-methanyl sulfonate.

It is provided by the present invention it is a kind of have hybrid cross-linked dynamic aggregation object foamed material can be soft, semi-rigid or Person's rigid foam.Foam can have water or it is anhydrous under the conditions of prepare, foaming method can be physical blowing, chemistry hair One of bubble, mechanical foaming are a variety of.Further, it is non-reacted that suitable auxiliary type known in the art can be used in foam Foaming agent.

A kind of preparation method of dynamic aggregation object foamed material of the invention includes the following steps: in preparation single network When dynamic aggregation object foamed material, reaction mass component A and reaction mass component B is first independently made；Reaction mass component A It is by 8 parts~20 parts of polyol compound, 0.05 part~1.0 parts of chain extender, 0.05 part~1.0 parts of crosslinking agent, organic metal class 0.01-0.5 parts of catalyst, 0.01-0.5 parts of amines catalyst, in 5-35 DEG C of material temperature, the condition of mixing speed 50-200r/min Under stir evenly it is obtained；Reaction mass component B is by 10 parts~20 parts of polyisocyanate compound, foaming agent 0.5 part~3.5 Part, 0.05 part~0.2 part of foam stabiliser, the system of stirring evenly under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature ?；Then reaction mass component A is mixed with reaction mass component B according to 1.0~1.5:1 mass ratio, it is quick through professional equipment Stir to get the single network dynamic aggregation object of foaming.Finally, the single network dynamic aggregation object after foaming is added to mold In, solidify 30min~60min at room temperature, then solidifies at high temperature and steeped to get to the dynamic aggregation object based on single network Foam material.At least one component contains ligand groups in the component A and component B.It is cured as at a high temperature of described in temperature Degree is solidifies 6h at 60 DEG C, or in temperature is 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.Above-mentioned polyol compound In hydroxyl (OH) group and polyisocyanate compound in isocyanates (NCO) group molar ratio may make it is final poly- Urethane foam is free of free-end NCO group.The molar ratio of NCO/OH is preferably 0.9/1 to 1.2/1.NCO/OH is 1/1 Molar ratio correspond to isocyanate index be 100.In the case where water is used as foaming agent, the isocyanate index is preferably big In 100, such isocyanate groups can be reacted with water.

In dynamic aggregation object foamed material preparation method of the invention, binary hybrid crosslinking dynamic aggregation object foam is being prepared When material, the step of according to above-mentioned preparation single network dynamic aggregation object, the 1st network is first prepared；Then the 2nd network mistake is being prepared The 1st network is added in the reaction mass A ' by Cheng Zhong, i.e., reaction mass component A ' at this time be 8 parts~20 parts of polyol compound, 0.05 part~1 part of chain extender, 0.05 part~0.4 part of crosslinking agent, 0.01~0.5 part of organometallic catalysts, amines catalyst 0.01~0.5 part, the 1st 0.1 part of network polymer~15 parts, under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature It stirs evenly obtained；Reaction mass component B ' is 10 parts~20 parts of polyisocyanate compound, 2 parts of foaming agent~3.5 parts, foam It 0.05 part~0.2 part of stabilizer, is stirred evenly under conditions of 5-50 DEG C of mixing speed 50-200r/min of material temperature obtained.Then Reaction mass component A ' is mixed with reaction mass component B ' according to 1.0~1.5:1 mass ratio, is quickly stirred through professional equipment To the hybrid cross-linked dynamic aggregation object of foaming.Finally, the hybrid cross-linked dynamic aggregation object after foaming is added in mold, in room Temperature is lower to solidify 30min~60min, then solidifies at high temperature to get to based on hybrid cross-linked dynamic aggregation object foamed material. At least one component contains ligand groups in the component A ' and component B '.Be cured as at a high temperature of described be in temperature Solidify 6h at 60 DEG C, or in temperature be 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.And so on, it is miscellaneous in preparation ternary When changing crosslinking dynamic aggregation object foamed material, the 1st network and the 2nd network are first prepared, then when preparing 3 network, the 1st net is added Network and the 2nd network are sufficiently mixed and foam.

In the preparation process of hybrid cross-linked dynamic aggregation object, the additive amount of dynamic aggregation object each component raw material is not done Special to limit, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

Dynamic aggregation object foamed material provided by the present invention further relates to: by welding, gluing, cutting, matching plane, perforation, The dynamic aggregation object foamed material, is transformed into any shape that needs by coining, lamination and hot forming, for example, pipe, stick, Sheath, container, ball, piece, volume and band；Purposes of the dynamic aggregation object foamed material in floating installation；By lamination, bonding, Fusion and other interconnection technique, by the dynamic aggregation object foamed material and sheet material, film, foam, fabric, stiffener with And other materials known to those skilled in the art are combined into complicated interlayer structure together；The dynamic aggregation object foam Purposes of the material in washer or sealing；The purposes of the dynamic aggregation object foamed material in packaging material or in a reservoir.It closes In dynamic aggregation object of the invention, foamable dynamic aggregation object is such a type, allow to by extrusion, injection molding, Other forming techniques known to compression moulding or those of skill in the art deform them.

Dynamic aggregation object of the invention is due to containing covalent cross-linking and good dynamic characteristics π-π stacking work more than gel point With dynamic aggregation object obtained all has certain stability and self-healing properties.Covalent cross-linking maintains dynamic poly- well The balanced structure of object is closed, simultaneously because the presence of supermolecular mechanism, can be used as can sacrifice the toughness that key increases material.For example, By suitable component selection and formula design, the polymer with good plasticity can be prepared and block glue；Based on oversubscription The dynamic reversibility of son effect can design and prepare material with shape memory and self-repair function and toughness is splendid Thin polymer film, fiber or plate have extensive in fields such as bio-medical material, military affairs, aerospace, the energy, buildings Purposes；In addition, the sensor etc. to stress sensitive can be prepared using its dynamic.

Dynamic aggregation object material of the present invention is described further below with reference to some specific embodiments.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.

Embodiment 1

100 mass parts toluene, 36 mass parts acrylamides, 7.2 mass parts 1H, 1H, 2H- seven are added in No. 1 reactor Amyl fluoride -1- alkene, 0.1 mass parts azodiisobutyronitrile, 0.01 mass parts tetramethylethylenediamine (TEMED), are uniformly mixed, It is warming up to 80 DEG C, after reacting 2h, 24 mass parts toluene di-isocyanate(TDI)s (TDI) is added, remove solvent after the reaction was continued 2h, be used in combination Deionized water is cleaned as far as possible, and then product is put into 100 mass parts deionized waters, 12h is swollen at room temperature, obtains one kind Dynamic aggregation object hydrogel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, is carried out using cupping machine Extension test, rate of extension 50mm/min, measuring sample tensile strength is 1.12 ± 0.15MPa, and elongation at break is 245.21 ± 23.17%, can be made into a kind of tack carry medicine stiff gel material carry out using.

Embodiment 2

By polyacrylonitrile (average molecular weight about 10000) 1 molar equivalent, 5 molar equivalent of 3- (azido-methyl) pyridine, 2,5- 10 molar equivalent of dehydration -1- nitrine -1- deoxy-D-glucose alcohol, 3 molar equivalent of nitrine methyl acetate, 100 moles of zinc chloride Equivalent and a small amount of fumed silica and nanoscale ferroso-ferric oxide are dissolved in dimethylformamide, and ultrasound 5min makes respectively at room temperature Component is warming up to 125 DEG C after being sufficiently mixed uniformly and is stirred to react, and obtains modified polyacrylonitrile product 1；Modified polyacrylonitrile is produced The 1 of 0.5 times of molar equivalent of the sum of object 1 and institute's hydroxyl, hexamethylene-diisocyanate reacts in dimethyl sulfoxide, is crosslinked Modified polyacrylonitrile product 2；The DMSO solution containing trifluoromethanesulfonic acid iron is added in suitable modified polyacrylonitrile product 2, Swelling 12h is stirred evenly and stood, a kind of dynamic aggregation object organogel is made.The organogel can also be made in externally-applied magnetic field Certain shape memory characteristic is shown under, can be made a kind of shape-memory material carry out using.

Embodiment 3

36 mass parts 3- butene-1-ols are added in No. 1 reactor, 7.8 mass parts allylurea -2- fluorenes (utilize 2- ammonia Base fluorenes and allyl isocyanate reaction be made), 2.3 mass parts sodium acrylate, 0.1 mass parts potassium peroxydisulfate (KPS), 0.12 mass After being stirred to react 1h at room temperature, 3 mass parts two are added in part N, N- dimethylformamide (DMF), 150mL dimethyl sulfoxide DMSO 60 mass parts methyl diphenylene diisocyanates (MDI), 0.7 mass parts triethylamine are added after mixing in luxuriant nickel polymer, After mixing, after being warming up to 60 DEG C of reaction 2h, solvent is removed, and be washed with deionized water product, then places it in 100 Swelling is stood for 24 hours in mass parts phthalic acid ethyl alcohol ester and 2 mass parts pyridine mixed solutions, obtains a kind of dynamic aggregation object Plasticizer swell gel.The plasticizer swell gel can show different mechanical properties, body according to the speed of action of external force Now impact the effect being hardened, there is good toughness and self-repairability, can be used for manufacturing a kind of toughness material carry out using.

Embodiment 4

Allyl carbamate -6- the anthanthrene that 0.3 molar equivalent is added in No. 1 reactor (utilizes 6- methylol Anthanthrene and allyl isocyanate reaction be made), the methacryl trimethyl ammonium chloride of 1 molar equivalent, 0.005 molar equivalent Potassium peroxydisulfate (KPS), 0.005 molar equivalent N, N- dimethyl cyclohexyl amine, enough methylene chloride, are warming up to 50 DEG C and are stirred to react After 4h, solvent is removed, product 1 is made；By 50 mass parts products 1,35 mass parts acrylamides, 0.5 mass parts AIBN, 0.5 Mass parts TEMED mixing is dissolved in 100 mass parts toluene, and after being warming up to 80 DEG C of reaction 2h, 40 mass parts TDI are added, and is continued anti- After answering 2h, solvent is removed, after being washed with deionized water, the 1- ethyl -3- methyl of 5 mass parts graphenes and 50 mass parts is added Tetrafluoroborate ionic liquid, ultrasonic wave dispersion stand for 24 hours after mixing evenly, then remove solvent, obtain one kind Dynamic aggregation object ionic liquid swell gel.The ionic liquid swell gel has good electric conductivity and mechanical property, can incite somebody to action It is made the supercapacitor with self-healing properties carry out using.

Embodiment 5

3- allyl -5- methyl-1 H- the pyrrole of 10 mass parts methyl acrylates, 5.5 mass parts is added in No. 1 reactor Cough up simultaneously [2,3-b] pyridine, 0.12 mass parts methyl ethyl ketone peroxide, the 4-dimethylaminopyridine of 0.12 mass parts, 180 mass parts Chloroform after being stirred to react 1h at room temperature, is added 50 mass parts tetrahydrofurans (THF) and continues to stir 12h, then most with deionized water Amount washes away THF, obtains product 1；10 mass parts products 1,10 mass parts polyethylene glycol (molecular weight are added in No. 2 reactors About 1000), after being completely dissolved mixing, 5 mass parts polymethylene polyphenyl polyisocyanic acid are added in 20 parts by mass Methylene chloride Ester, 0.2 mass parts triethylamine, 0.1 mass parts copper chloride, 0.5 mass parts glass microballoon are warming up to 80 after ultrasonic wave dispersion DEG C, after the reaction was continued 2h, 30 mass parts alkyl-blocked polyethylene glycol oligomer and 0.5 mass parts caddy is added, mixing is equal Solvent is removed after even, and blend is placed in mold, 12 hours is kept the temperature at 80 DEG C, a kind of dynamic aggregation object oligomerisation is obtained after cooling Object swell gel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carries out stretching survey using cupping machine Examination, rate of extension 50mm/min, measure sample tensile strength be 4.42 ± 0.79MPa, elongation at break be 213.43 ± 32.74%, the selfreparing sealing material with excellent sealing effect can be made into.

Embodiment 6

1 molar equivalent containing hydrogen silicone oil (average molecular weight about 20000, the repetitive unit of siliceous hydrogen are added in No. 1 reactor Molar ratio with the repetitive unit of not siliceous hydrogen is about 1:2), the quaternary ammoniums of 15 molar equivalent allylureas and silicone oil gross mass 7% Alkali, which is sufficiently mixed, to be placed in mold, is warming up to 170 DEG C, keeps the temperature 10 minutes, and product 1 is made after cooling；Add in No. 2 reactors Enter 1 molar equivalent containing hydrogen silicone oil (average molecular weight about 20000, the repetitive unit of siliceous hydrogen and the repetitive unit of not siliceous hydrogen Molar ratio is about 1:2), 25 molar equivalent acrylonitrile, (perfluoro hexyl) ethylene of 2 molar equivalents, silicone oil gross mass 7% quaternary ammonium Alkali, which is sufficiently mixed, to be placed in mold, is warming up to 170 DEG C, keeps the temperature 10 minutes, and product 2 is made after cooling；By 20 mass parts products 1,15 mass parts products 2,10 mass parts containing hydrogen silicone oils (average molecular weight about 20000, the repetitive unit of siliceous hydrogen and not siliceous hydrogen The molar ratio of repetitive unit be about 1:2), the quaternary ammonium of 2 mass parts crosslinking agent bi-vinyls sealing end silicone oil and silicone oil gross mass 7% Alkali is sufficiently mixed to be placed in mixer and is kneaded, and 1 mass parts of carbon black, 1 mass parts glass fibre is added, after being kneaded 6h, Taking-up is placed in mold, and a kind of dynamic aggregation object elastomer is made after cooling.It, can foundation with good intensity and plasticity Die size is prepared into product of different shapes.After the cutting of this elastomer, applies good pressure 1-2h in section part, break Face can voluntarily bond, and form again.Using its functional characteristic, deceleration driven can be applied to.In pulling force Under effect, the synergistic action effect between dipole-dipole effect and hydrogen bond action makes the tensile strength of the dynamic aggregation object and breaks It splits elongation and has obtained certain promotion, mechanical property is more preferable.When the material is under higher temperature, dipole-dipole is made With decrease, synergistic effect decline, at different temperature, which can show orthogonal mechanics effect.

Embodiment 7

Polyethers ketone powder, the 0.01 molar equivalent condensing agent that 1 molar equivalent side group contains carboxyl are added in No. 1 reactor I-hydroxybenzotriazole (HOBT) and 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt Hydrochlorate (EDC), is dissolved in enough toluene, and after mixing, the 2 of 0.4 times of carboxyl molar equivalent are added in stirring to dissolution, and 3,4, The aniline of 5,6- pentafluoroanilines and 0.4 times of carboxyl molar equivalent continues at room temperature after being stirred to react 12h, and 0.2 times of carboxylic is added The 1,4-Diaminobutane of base molar equivalent after the reaction was continued 6h, removes solvent, it is spare that product 1 is made；In No. 2 reactors Polyethers ketone powder, the 0.01 molar equivalent condensing agent I-hydroxybenzotriazole (HOBT) that 1 molar equivalent side group contains carboxyl is added With 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), it is dissolved in enough Toluene, stirring to dissolution after mixing, are added the 1,4-Diaminobutane of 0.5 times of carboxyl molar equivalent, continue at room temperature After being stirred to react 12h, solvent is removed, product 2 is made；By 30 mass parts products 1, the 20 mass parts polyethers of mass parts product 2 and 50 Ketone mixing, and 3 mass parts glass fibres, 1 mass parts nano talc are added, after extruding pelletization is molded, it is made a kind of dynamic State polymer ordinary solid.The dumbbell shape batten for taking 80.0 × 10.0 × 2.0mm size carries out stretching survey using cupping machine Examination, rate of extension 10mm/min, measure sample tensile strength be 67.53 ± 6.25MPa, elongation at break be 57.56 ± 5.63%, using its surface hardness and high intensity, a kind of selfreparing plate use, surface scratch meeting can be made into It is automatically repaired healing.

Embodiment 8

The bromo- 1- butylene of 5.6 mass parts 4-, 8.4 mass parts 3- butene-1-ols, 15 mass parts third are added in No. 1 reactor Olefin(e) acid ethyl ester, 0.5 mass parts azodiisobutyronitrile and 0.1 mass parts TEMED are warming up to 90 DEG C, the reaction was continued after mixing evenly Then 4 mass parts TDI and 0.05 mass parts triethylamine are added in 4h, after the reaction was continued 2h, product 1 is made；In No. 2 reactors 100 mass parts polyether polyol SA-460 (hydroxyl value 445-475) are added, 17 mass parts isopropyl isocyanates are warming up to 80 DEG C, instead After answering 1h, 100 DEG C are warming up to, product 2 is made after reacting 2h；By the product 1 of 20 mass parts, 100 mass parts products 2,1 mass parts Diethyl toluene diamine (DETDA), the dibutyl tin dilaurate (DY-12) of 0.5 mass parts, the TDI of 50 mass parts, 4 matter Part water, 2 parts by mass Methylene chloride, 0.5 mass parts carbon nanotube, 5 mass parts graphenes are measured, it is suitable to be put into after being dispersed with ultrasonic wave Mold in, after mixing with professional blender, be warming up to 80 DEG C, so that it is reacted and is foamed, after the completion of foaming extremely by foam Continue to cure 6h in 60 DEG C of baking ovens, obtains a kind of dynamic aggregation object foamed material, it is made into 20.0 × 20.0 × The bulk sample of 20.0mm size carries out compression performance test using universal testing machine, and compression speed 2mm/min measures sample 10% compressive strength of product is 6.34 ± 0.63MPa.Obtained polymer foams light specific gravity, intensity are good, easily molded, can be by it Antistatic backing as electronic device carry out using.

Embodiment 9

In No. 1 reactor, the sodium alginate of 1 molar equivalent is taken to be dissolved in enough deionized waters, is then added 0.5 and rubs The NaIO of your equivalent₄, after room temperature is protected from light stirring 6h, the ethylene glycol that 0.5 molar equivalent is added continues to stir 1h, rotates by dialysis Afterwards, the sodium alginate of theoretical oxidation degree about 50% is made；In No. 2 reactors, 1.5 mass parts theoretical oxidation degree are added about 50% sodium alginate is dissolved in enough PBS buffer solution, and 6.2 mass parts β-guanidinopropionic acid is then added, and continues to stir 6h Afterwards, after being stirred, mixed liquor is put into after standing 12h in 20 DEG C of insulating boxs, product 1 is made；10 are added in No. 2 reactors Mass parts product 1,10 mass parts polyacrylamides (molecular weight 1000), 3 mass parts hexamethylene diisocyanates, 0.1 mass parts Triethylamine is warming up to 80 DEG C of reaction 2h, 50 mass parts deionized waters is added after reaction, mixed liquor is put after mixing Enter after standing 12h in 20 DEG C of insulating boxs, a kind of dynamic aggregation object hydrogel is made.The dynamic aggregation object hydrogel has good Toughness is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carries out extension test using cupping machine, draws Stretch rate be 50mm/min, measure sample tensile strength be 2.53 ± 0.58MPa, elongation at break be 569.32 ± 78.35%, can be made into a kind of adhesive with self-healing properties carry out using.

Embodiment 10

In No. 1 reactor, the sodium alginate of 1 molar equivalent is taken to be dissolved in enough deionized waters, is then added 0.5 and rubs The NaIO of your equivalent₄, after room temperature is protected from light stirring 6h, the ethylene glycol that 0.5 molar equivalent is added continues to stir 1h, rotates by dialysis Afterwards, the sodium alginate of theoretical oxidation degree about 50% is made；In No. 2 reactors, 5.5 mass parts theoretical oxidation degree are added about 50% sodium alginate is dissolved in enough PBS buffer solution, and 2.6 mass parts methylguanidines, 4.4 mass parts 3- bromos third are then added Amine continues after stirring 6h, 0.1 mass parts calcium chloride, 10 mass parts deionized waters is added, after being stirred, mixed liquor is put into After standing 12h in 20 DEG C of insulating boxs, product 1 is made；Obtained product 1,100 mass parts polyethers are added in No. 3 reactors Polyol E P-3600 (hydroxyl value 26-30), 0.3 mass parts N, N '-diethyl piperazine, 2 mass parts ethylenediamines (DA), 0.3 mass Part dibutyl tin dilaurate (DY-12), 1 mass parts organic silicone oil, 9 mass parts isoflurane chalcone diisocyanates, 5 mass parts Water, 4 parts by mass Methylene chloride are uniformly mixed, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, after foaming By foam as curing 6h is continued in 60 DEG C of baking ovens, a kind of dynamic aggregation object foamed material is obtained after cooling.It is made into The bulk sample of 20.0 × 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2mm/min, measuring 50% compressive strength of sample is 2.91 ± 0.53MPa.Obtained polymer foams light specific gravity, resilience It is good, can be made into thermal insulation material carry out using.

Embodiment 11

The 3- butene-1-ol of 1 molar equivalent, the acrylonitrile of 1 molar equivalent, 1 molar equivalent are added in No. 1 reactor The bromo- 1- butylene of 4-, the potassium peroxydisulfate of 0.01 molar equivalent and the TEMED of 0.01 molar equivalent, and be added enough toluene by its Stirring and dissolving, then heats to 50 DEG C, and after reacting 4h, 87 mass parts TDI and 0.1 mass parts triethylamine is added, the reaction was continued 2h, Solvent is removed, product 1 is made；100 mass parts polyether polyol EP-330N (hydroxyl value 32-36), 30 are added in No. 2 reactors Mass parts product 1,3 mass parts foam microspheres, the N-ethylmorpholine of 0.5 mass parts, the MDI of 8 mass parts, 3 mass parts water, 3 matter Part methylene chloride is measured, is uniformly mixed, is warming up to 80 DEG C, is quickly stirred to react with the blender of profession, by foam after foaming As for curing 6h is continued in 60 DEG C of baking ovens, a kind of dynamic aggregation object foamed material is obtained after cooling.It is made into 20.0 × The bulk sample of 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2 mm/min, Measuring 50% compressive strength of sample is 5.41 ± 0.95MPa.Obtained polymer foams light specific gravity, resilience be good, Yi Cheng Type, can be made into automotive interior material carry out using.

Embodiment 12

Polyethers ketone powder, the 0.01 molar equivalent condensing agent that 1 molar equivalent side group contains carboxyl are added in No. 1 reactor I-hydroxybenzotriazole (HOBT) and 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt Hydrochlorate (EDC), is dissolved in enough toluene, and after mixing, the 3- amino of 0.3 times of carboxyl molar equivalent is added in stirring to dissolution Ethyl propionate continues at room temperature after being stirred to react 12h, adds the aminobenzene and 0.3 times of carboxyl of 0.4 times of carboxyl molar equivalent 1- pentafluorophenyl group -2- the thiocarbamide of molar equivalent, the reaction was continued 12h remove solvent, and it is spare that product 1 is made；In No. 2 reactors Polyethers ketone powder, the 0.01 molar equivalent condensing agent I-hydroxybenzotriazole (HOBT) that 1 molar equivalent side group contains carboxyl is added With 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), it is dissolved in enough Toluene, stirring to dissolution after mixing, are added the 1,4-Diaminobutane of 0.5 times of carboxyl molar equivalent, continue at room temperature After being stirred to react 12h, solvent is removed, product 2 is made；10 mass parts of mass parts product 1 and 50 products 2 are mixed, and are added 3 A kind of dynamic aggregation object ordinary solid is made after extruding pelletization is molded in mass parts glass fibre, 3 mass parts carbon fibers.It takes The dumbbell shape batten of 80.0 × 10.0 × 2.0mm size carries out extension test using cupping machine, and rate of extension is 10 mm/ Min, measuring sample tensile strength is 41.34 ± 2.45MPa, and elongation at break is 85.32 ± 7.92%, and utilization is its Surface hardness and high intensity, can be made into a kind of selfreparing plate, and surface scratch can be automatically repaired healing.

Embodiment 13

1 molar equivalent [6- phenyl -2,2'- bipyridyl] -4- carboxylic acid, 1 molar equivalent allyl is added in No. 1 reactor Isocyanates, 0.01 molar equivalent triethylamine after being substantially soluble in sufficient toluene, are warming up to 80 DEG C, react 2h, then remove molten Compound 1 is made in agent；5 mass part compounds 1,0.2 mass parts NaOH are mixed and are dissolved in 10 mass parts DMSO, under ice bath 30 mass parts ethyl acrylates are added, lead to nitrogen deoxygenation after, be added 0.02 mass parts potassium peroxydisulfate, 0.01 mass parts TEMED, 0.01 mass parts platinum chloride, 0.5 mass parts glass fibre after being quickly stirred, are warming up to 60 DEG C, remove after reaction 4h molten A kind of dynamic aggregation object elastomer is made in agent.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, utilizes drawing It stretches testing machine and carries out extension test, rate of extension 50mm/min, measuring sample tensile strength is 4.42 ± 0.73MPa, fracture Elongation is 368.32 ± 52.63%.The product can be prepared into a kind of tough elastomer material carry out using.

Embodiment 14

100 mass parts polyether polyol EP-560 (hydroxyl value 290-310) are added in No. 1 reactor and are warming up to 80 DEG C, add Enter 7.2 mass parts (iodomethyl) ethylene oxide, 0.1 mass parts sodium hydroxide, be warming up to 100 DEG C, product 1 is made after reacting 2h； Obtained product 1, bis- (2- dimethylaminoethyl) ethers of 0.5 mass parts, 2 mass parts MOCA, 0.4 are added in No. 4 reactors Mass parts DY-300,0.8 mass parts organic silicone oil, the MDI of 30 mass parts, 4 mass parts water, 7 mass parts foam microspheres, 4 mass Part methylene chloride, is uniformly mixed, is warming up to 80 DEG C, is quickly stirred to react with the blender of profession, after foaming extremely by foam Continue to cure 6h in 60 DEG C of baking ovens, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into 20.0 × 20.0 The bulk sample of × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2 mm/min, is measured 50% compressive strength of sample is 3.58 ± 0.48MPa.Obtained polymer foams light specific gravity, resilience are good, can be made At stationery material carry out using.

Embodiment 15

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 2,3,4,5,6- five fluoro benzyl alcohols of 1 molar equivalent are added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made； The 1 of 1 molar equivalent is added in No. 2 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is uniformly mixed Afterwards, the benzyl alcohol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 2 is made；It is added in No. 4 reactors 100 mass parts polyether polyol EP-3600 (hydroxyl value 26-30), 3.7 mass part compounds 1,2.7 mass part compounds 2, heating To 80 DEG C, product 1 is made after reacting 2h；Obtained product 1,1 mass parts triethylamine, 3 mass are added in No. 5 reactors Part ethylenediamine (DA), 0.5 mass parts modified triethylene diamine solution (DY-8154), 1 mass parts organic silicone oil, 5 mass parts water, 4 parts by mass Methylene chloride, 4 mass parts MDI are uniformly mixed, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, send out It soaks foam after type as continuing to cure 6h in 60 DEG C of baking ovens, obtains a kind of dynamic aggregation object foamed material after cooling.It will Its bulk sample that 20.0 × 20.0 × 20.0mm size is made carries out compression performance test, compression speed using universal testing machine Rate is 2mm/min, and measuring 50% compressive strength of sample is 3.12 ± 0.34MPa.Obtained polymer foams light specific gravity, matter Ground is softer, resilience is good, can be made into automotive interior material carry out using.

Embodiment 16

1 molar equivalent is added in No. 1 reactor to work as containing vinyl silicone oil, 0.01 molar equivalent irgasfos 168,5 moles Trimethyl (2- mercaptoethyl) ammonium, 5 molar equivalent 4- mercaptopyridines, 10 molar equivalent toluene are measured, is placed it in after mixing The ultraviolet equal lower irradiation 30min of 300W, removes solvent, product 1 is made after taking-up；Take 20 mass parts products 1,3 mass parts AC foaming Agent, 1 mass parts barium stearate, 2 mass parts expandable particles, in mixing 30min on open mill, then blend glue stuff taking-up is put into In suitable mold, foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, and clamp time is Foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h, obtains dynamic aggregation after cooling by 10-15min, pressure 10MPa Object foamed material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compressibility using universal testing machine It can test, compression speed 2mm/min, measuring 50% compressive strength of sample is 1.87 ± 0.35MPa.Obtained foam of polymers Material proportion is light, elasticity is good, and the pore structure of half-open semi-closure makes it have the characteristic of low resilience, can be made into a kind of cloth occasionally filling Material carry out using.

Embodiment 17

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the 2- iodoacetamide of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is anti-at No. 2 It answers and 100 mass parts polyether polyol EP-553 (hydroxyl value 54-58), 10 mass part compounds 1 is added in device, be warming up to 80 DEG C, instead After answering 1h, 2 mass parts ethyl isocyanates are added, product 1 is made after the reaction was continued 2h；Obtained by being added in No. 3 reactors Product 1,1 mass parts triethanolamine, 3 mass parts 1,4- butanediols (BDO), 0.5 mass parts organo-bismuth (DY-20), 1 mass parts Organic silicone oil, 3 mass parts water, 7 parts by mass Methylene chloride, 5 mass parts MDI are uniformly mixed, are warming up to 80 DEG C, with stirring for profession It mixes device to be quickly stirred to react, by foam as curing 6h is continued in 60 DEG C of baking ovens after foaming, be obtained after cooling a kind of dynamic State polymer foams.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, is carried out using universal testing machine Compression performance test, compression speed 2mm/min, measuring 50% compressive strength of sample is 3.42 ± 0.66MPa.Obtained polymerization Object foamed material light specific gravity, quality are softer, resilience is good, luggage box material carry out using.

Embodiment 18

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 2,4,6- trimethyl benzylalcohols of 1 molar equivalent are added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；? The 1 of 1 molar equivalent is added in No. 2 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent adds after mixing 7- amino -3- methyl -3,4- dihydro -1H- benzo [e] [Isosorbide-5-Nitrae] diazepine -2, the 5- diketone for entering 1 molar equivalent, is warming up to 80 DEG C, it is stirred to react 2h, compound 2 is made；100 mass parts polyether polyol HPOP40 (hydroxyl value 20- are added in No. 3 reactors 23), 3.2 mass part compounds 1,4.3 mass part compounds 2 are warming up to 80 DEG C, and after reacting 1h, 1.5 mass parts 2,3- are added Epoxypropyltrimethylchloride chloride and 0.01 mass parts sodium hydroxide are warming up to 100 DEG C, and product 1 is made after reacting 2h；At No. 6 Obtained product 1,1 mass parts N, N- dimethyl benzylamine, 3 mass parts trimethylolpropanes, 0.5 mass parts are added in reactor Dibutyl tin dilaurate (DY-12), 1 mass parts organic silicone oil, 4 mass parts water, 6 parts by mass Methylene chloride, 7 mass parts MDI, It is uniformly mixed, is warming up to 80 DEG C, be quickly stirred to react with the blender of profession, by foam as 60 DEG C of baking ovens after foaming In continue to cure 6h, obtain a kind of dynamic aggregation object foamed material after cooling.It is made into 20.0 × 20.0 × 20.0 mm rulers Very little bulk sample carries out compression performance test using universal testing machine, and compression speed 2mm/min measures the pressure of sample 50% Contracting intensity is 4.67 ± 0.52MPa.Obtained polymer foams light specific gravity, resilience are good, can be made into shape memory Foamed material carry out using.

Embodiment 19

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the pyridazine -3- methanol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is anti-at No. 3 It answers and 100 mass parts polyether polyol EP-455S (hydroxyl value 43.5-46.5), 3.3 mass part compounds 1 is added in device, be warming up to 80 DEG C, after reacting 1h, 1.5 mass parts oxirane carboxylic acid sylvite and 0.01 mass parts sodium hydroxide is added, is warming up to 100 DEG C, Product 1 is made after reacting 2h；Obtained product 1,0.5 mass parts triethylamine, 3 mass parts diethyls are added in No. 4 reactors Ethylaminoethanol (DEAE), 0.5 mass parts organo-bismuth (DY-20), 1.3 mass parts organic silicone oils, 3 mass parts water, 4 mass parts dichloros Methane, 5 mass parts isophorone diisocyanate (IPDI) are uniformly mixed, are warming up to 80 DEG C, are quickly stirred with the blender of profession It mixes reaction, after foaming foam is obtained into a kind of dynamic aggregation object bubble as continuing to cure 6h in 60 DEG C of baking ovens after cooling Foam material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compression performance survey using universal testing machine Examination, compression speed 2mm/min, measuring 50% compressive strength of sample is 4.31 ± 0.56MPa.Obtained polymer foams Light specific gravity, resilience are good, can be made into foam encapsulating material carry out using.

Embodiment 20

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the bromo- 1- propyl alcohol of 2,3- bis- of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；3 100 mass parts polyether polyol ED-28 (hydroxyl value 26.5-29.5), 3.7 mass part compounds 1 are added in number reactor, are warming up to 80 DEG C, product 1 is made after reacting 2h；Obtained product 1,1 mass parts N, N- dimethyleyelohexane are added in No. 5 reactors Amine, 2 mass parts ethylenediamines (DA), 0.5 mass parts DY-215,1 mass parts organic silicone oil, 6 mass parts water, 7 mass parts dichloromethanes Alkane, 4 mass parts 1, hexamethylene-diisocyanate (HDI) are uniformly mixed, are warming up to 80 DEG C, are quickly stirred instead with the blender of profession It answers, foam is obtained into a kind of dynamic aggregation object foam material after cooling as curing 6h is continued in 60 DEG C of baking ovens after foaming Material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compression performance test, pressure using universal testing machine Contracting rate is 2mm/min, and measuring 70% compressive strength of sample is 1.13 ± 0.21MPa.Obtained polymer foams specific gravity Gently, soft, resilience is good, can be made into cloth idol interior packing material carry out using.

Embodiment 21

Isosorbide-5-Nitrae-fourth diisocyanate of 1 molar equivalent, the triethylamine of 0.01 molar equivalent are added in No. 1 reactor, rises Piperazine -1- the carbonamidine into 1 molar equivalent is slowly added dropwise to after 80 DEG C in temperature while stirring, the reaction was continued after being added dropwise 1h, system Obtain compound 1；Isosorbide-5-Nitrae-fourth diisocyanate of 1 molar equivalent, the triethylamine of 0.01 molar equivalent are added in No. 2 reactors, After being warming up to 80 DEG C, the pyridine -4- methanol into 1 molar equivalent is slowly added dropwise while stirring, the reaction was continued after being added dropwise 2h, system Obtain compound 2；100 mass parts polyether polyol DD-380A (hydroxyl value 360-400), 0.5 mass parts are added in No. 3 reactors After being warming up to 80 DEG C, after the reaction was continued 2h, 5 mass parts are added in triethylamine, 37 mass part compounds 1,34 mass part compounds 2 AC foaming agent, 10 mass parts sorbierites, 5 mass parts [2,3,5,6- tetra- { (diethylamino) methyl } phenylene -1,4- bis- (three Fluorine methanesulfonic acid palladium)], 34 mass parts TDI, the 1 miscellaneous benzene of mass parts ruthenium, be warming up to 80 DEG C, after abundant cross-linking reaction, cross-linking products taken Out as in mold, foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, and clamp time is 10-15min, pressure 10MPa finally obtain dynamic aggregation object foamed material, with good rigidity and intensity.It is made At the bulk sample of 20.0 × 20.0 × 20.0mm size, compression performance test is carried out using universal testing machine, compression speed is 2mm/min, measuring 10% compressive strength of sample is 17.45 ± 1.53MPa.Obtained polymer foams light specific gravity, size Stability is good, can be lauched as tank buoyant material carry out using.

Embodiment 22

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, 2- (methylol) anthracene of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；At No. 2 The 1 of 1 molar equivalent is added in reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is added 1 after mixing The 2 of molar equivalent, 3,4,5,6- five fluoro benzyl alcohols, are warming up to 80 DEG C, are stirred to react 2h, and compound 2 is made；In No. 3 reactors 100 mass parts polyether polyol DL-400 (hydroxyl value 270-290) and 0.5 mass parts triethylamine are added, 38 are added after mixing Mass part compound 1,18 mass part compounds 2,17 mass parts isopropyl isocyanates, are warming up to 80 DEG C, after the reaction was continued 2h, system Obtain product 1；Obtained product 1,100 mass parts polyether polyol MN-3050DF (hydroxyl value 54- are added in No. 4 reactors 57), 5 mass parts 3- amido-1,2-propanediols, 15 mass parts epoxidized soybean oils, mass parts KH550,70 mass parts kaolin, 2 Mass parts glass fibre, 1 mass parts fumed silica, 4 mass parts UV-531,10 mass parts pentachlorophenols, 2 mass parts February Dilaurylate is added 50 mass parts MDI, stirs evenly, mixed liquor is placed in mold after mixing, dries at 50 DEG C 4h is stood in case, and a kind of dynamic aggregation object elastomeric material is made after taking out cooling.It is made into 80.0 × 10.0 × 2.0mm ruler Very little dumbbell shape batten carries out extension test using cupping machine, and rate of extension is 50 mm/min, measures sample and stretches by force Degree is 18.34 ± 1.23MPa, and elongation at break is 325.23 ± 67.35%.The product can be prepared into a kind of deceleration driven It carries out using can be realized the effect being automatically repaired in impaired cracking.Under the action of pulling force, benzene-fluorobenzene effect and hydrogen bond Synergistic action effect between effect makes the tensile strength of the dynamic aggregation object and elongation at break obtain certain promotion；When When the product is in polar solvent, hydrogen bond action weakens, the mechanical properties decrease of polymer, in polar solvent environment In, benzene-fluorobenzene effect and hydrogen bond action show orthogonal mechanics effect.

Embodiment 23

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the 3- aminopropionitrile of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is anti-at No. 2 It answers and the 1 of 1 molar equivalent is added in device, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is added 1 after mixing 2- (methylol) naphthalene of molar equivalent, is warming up to 80 DEG C, is stirred to react 2h, and compound 2 is made；1 is added in No. 3 reactors to rub The 2,3 of 1 molar equivalent are added after mixing in the 1 of that equivalent, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent, 4,5,6- five fluoro benzyl alcohols, are warming up to 80 DEG C, are stirred to react 2h, and compound 3 is made；100 mass parts are added in No. 4 reactors Polyether polyol EP-8000 (hydroxyl value 22-26) and 0.5 mass parts triethylamine, be added after mixing 3.7 mass part compounds 1, 19 mass part compounds 2,9 mass part compounds 3 are warming up to 80 DEG C, and after the reaction was continued 2h, product 1 is made；In No. 5 reactors Obtained product 1,1 mass parts N, N- dimethyl cyclohexyl amine, 2 mass parts triethylene glycols, 4 mass parts TDI is added, is uniformly mixed, 80 DEG C are warming up to, after reacting 2h, reaction solution taking-up is placed in mold, 100 mass parts diisooctyl phthalates are added (DIOP), after standing swelling for 24 hours in 30 DEG C of baking ovens, a kind of dynamic aggregation object plasticizer swell gel had both been made.Gel tool Have good toughness and anti-pressure ability, can be made into a kind of sealing material carry out using.

Embodiment 24

With 1 molar equivalent 4,4'- azo bis- (4- cyano amylalcohols) is initiator, using 4- amylene-1-ol as chain-transferring agent, with Stannous octoate is catalyst, causes 50 molar equivalent α-ring-opening polymerisation of the chloro- 6-caprolactone at 110 DEG C, obtains product 1.It will Resulting product 1 is dissolved in dimethylformamide, and the sodium azide of 2 molar equivalent of chlorine atom is added, and reaction obtains product 2, then One end of 0.6 times of molar equivalent of azido is added as the 1,4- of 0.2 times of molar equivalent of bipyridyl salt compounded of iodine and azido of alkynyl Diacetylene is dissolved in tetrahydrofuran, and under the catalysis of cuprous iodide and pyridine, reaction obtains product 3 at 35 DEG C.In 100 mass parts The irgasfos 168 of 2-5 mass parts is added in products therefrom 3, is sufficiently blended and is placed in mold, is pressed and molded, obtains one kind Dynamic aggregation object elastomer.This elastomer toughness is good, and has the selectivity of cation, can be used as shape-memory material It carries out using different shapes can be showed by mixing from different cations.

Embodiment 25

N-Methyl pyrrolidone, the 3g graphene oxide of 150mL are added in No. 1 reactor, after ultrasonic wave is uniformly dispersed, 4,4- diamino-diphenyl ether (ODA), the 2- bromine ethamine of 2.4g and the 5- amino-uracil of 2.4g of 4.6g is added, and is warming up to 80 DEG C, after being uniformly mixed, reactant is moved into hydro-thermal reaction container, is placed under 80 DEG C of baking ovens and reacts for 24 hours, reacted N-Methyl pyrrolidone is dispersed using ultrasonic wave by modified graphene oxide obtained after, is configured to the molten of 3.5mg/mL Liquid, it is spare；Be added in No. 2 reactors the N-Methyl pyrrolidone of 72mL, 3.2g 4,4- diamino-diphenyl ether (ODA), The modified graphene oxide solution of 6.3mL after being uniformly dispersed using ultrasonic wave, is added the 3,3', 4 of 4.8g in a nitrogen atmosphere, 4'- biphenyltetracarboxylic dianhydride (BPDA) is stirred to after being completely dissolved, and 13mL acetic anhydride, 10.5mL pyridine is added, and is uniformly mixed Afterwards, reactant is transferred in the mold of production film immediately, after reaction for 24 hours, obtains a kind of dynamic aggregation object film.By its It is cut into the dumbbell shape batten of 80.0 × 10.0 × (0.08 ± 0.02) mm sizes, extension test is carried out using cupping machine, draws Stretching rate is 50mm/min, and measuring sample tensile strength is 7.53 ± 0.73MPa, and elongation at break is 275 ± 45%.Sample is drawn It is recycled after disconnected, places it in mold and be bonded after 1-3h, can form a film, be reused again, it can will using its property It is used as a kind of recuperability antistatic film.

Embodiment 26

The 1 of 1 molar equivalent is added in No. 1 reactor, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent mixes After closing uniformly, the 3- iodine propyl alcohol of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 1 is made；It is reacted at No. 2 The 1 of 1 molar equivalent is added in device, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent is added 1 mole after mixing The 3- hydroxypropionitrile of equivalent, is warming up to 80 DEG C, is stirred to react 2h, and compound 2 is made；100 mass are added in No. 4 reactors Part polyether polyol EP-8000 (hydroxyl value 22-26) and 0.5 mass parts triethylamine, are added 3.5 mass part compounds after mixing 1,7.2 mass part compound 2 is warming up to 80 DEG C, and product 1 is made after reacting 2h；Obtained product is added in No. 5 reactors 1,1 mass parts N, N- dimethyl cyclohexyl amine, 2 mass parts triethylene glycols, 4 mass parts TDI are uniformly mixed, and are warming up to 80 DEG C, react 2h Afterwards, reaction solution taking-up is placed in mold, 100 mass parts diisooctyl phthalates (DIOP) is added, in 30 DEG C of baking ovens After standing swelling for 24 hours, a kind of dynamic aggregation object plasticizer swell gel had both been made.The gel has good toughness and resistance to compression energy Power, can be made into a kind of sealing material carry out using.

The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims

1. a kind of hybrid cross-linked dynamic aggregation object, which is characterized in that it contains the covalent cross-linking and at least one formed by covalent bond Kind selected from close metal function, halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, ion hydrogen bond action, The supermolecular mechanism of radical cation dimerization；Wherein, covalent cross-linking reaches covalent friendship at least one cross-linked network It is more than the gel point of connection.

2. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Also contain other supermolecular mechanisms in object, wherein other supermolecular mechanisms include dipole-dipole effect, hydrogen bond action, Metal-ligand effect.

3. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and contains covalent cross-linking and supermolecular mechanism simultaneously in this cross-linked network, wherein altogether Valence crosslinking the degree of cross linking more than its gel point, supermolecule provided by supermolecular mechanism crosslinking the degree of cross linking its gel point with It is upper or following.

4. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object only contains a cross-linked network, and contains covalent cross-linking and supermolecular mechanism and at least one simultaneously in this cross-linked network The other supermolecular mechanisms of kind, wherein the degree of cross linking of covalent cross-linking is more than its gel point, supermolecule provided by supermolecular mechanism The degree of cross linking of crosslinking is in its gel point above and below, the degree of cross linking of the crosslinking of supermolecular mechanism provided by other supermolecular mechanisms In its gel point above and below.

5. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and supermolecular mechanism simultaneously, wherein covalently hands over The degree of cross linking of connection reaches gel point or more, the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism its gel point with It is upper or following；Another cross-linked network only contains at least one other supermolecular mechanism, wherein other supermolecular mechanisms are mentioned The degree of cross linking of the supermolecule crosslinking of confession is more than its gel point.

6. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is in its gel point More than；Another cross-linked network contains supermolecular mechanism, wherein the friendship of the crosslinking of supermolecular mechanism provided by supermolecular mechanism Connection degree is more than its gel point.

7. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object contains there are two cross-linked network, one of cross-linked network contain the degree of cross linking of covalent cross-linking and covalent cross-linking its gel point with On；Another cross-linked network contains supermolecular mechanism, wherein the crosslinking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism Degree is more than its gel point；Also contain at least one other supermolecular mechanism at least one cross-linked network simultaneously, wherein its The degree of cross linking of the crosslinking of supermolecular mechanism provided by its supermolecular mechanism is in its gel point above and below.

8. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object cross-linked network containing there are three, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is in its gel point More than；Another cross-linked network only contains supermolecular mechanism, wherein the crosslinking of supermolecular mechanism provided by supermolecular mechanism The degree of cross linking is more than its gel point；Third cross-linked network only contains at least one other supermolecular mechanism, wherein other oversubscription Son acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.

9. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic aggregation Object cross-linked network containing there are two, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is in its gel point More than；Another cross-linked network contain the degree of cross linking of supermolecular mechanism and covalent cross-linking and covalent cross-linking its gel point with On, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below.

10. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object to contain there are two cross-linked network, one of cross-linked network contains the degree of cross linking of covalent cross-linking and covalent cross-linking in its gel point More than；Another cross-linked network contain the degree of cross linking of supermolecular mechanism and covalent cross-linking and covalent cross-linking its gel point with On, wherein the degree of cross linking of the crosslinking of supermolecular mechanism provided by supermolecular mechanism is in its gel point above and below；Simultaneously extremely Also contain at least one other supermolecular mechanism in a few cross-linked network, wherein oversubscription provided by other supermolecular mechanisms The degree of cross linking of son effect crosslinking is in its gel point above and below.

11. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contain to A few cross-linked network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and wherein at least one The noncrosslinking supermolecule polymer containing supermolecular mechanism is scattered in network.

12. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contain to A few cross-linked network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and wherein at least one The noncrosslinking supermolecule polymer containing supermolecular mechanism and at least one other supermolecular mechanism is scattered in network.

13. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contain to A few cross-linked network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and wherein at least one The existing cross-linked polymer containing supermolecular mechanism in granular form is scattered in network.

14. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contain to A few cross-linked network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and wherein at least one The existing cross-linked polymeric containing supermolecular mechanism and at least one other supermolecular mechanism in granular form is scattered in network Object.

15. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and simultaneously containing covalent cross-linking and close metal function in this cross-linked network, wherein For the degree of cross linking of covalent cross-linking more than its gel point, the degree of cross linking of the crosslinking of supermolecular mechanism provided by close metal function is solidifying at it Glue point above and below.

16. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and acted on simultaneously containing covalent cross-linking and benzene-fluorobenzene in this cross-linked network, In, more than its gel point, the degree of cross linking that benzene-fluorobenzene acts on provided supermolecular mechanism crosslinking exists the degree of cross linking of covalent cross-linking Its gel point above and below.

17. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and contain covalent cross-linking and ion hydrogen bond action simultaneously in this cross-linked network, In, the degree of cross linking of covalent cross-linking is more than its gel point, the degree of cross linking of the crosslinking of supermolecular mechanism provided by ion hydrogen bond action In its gel point above and below.

18. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and contain covalent cross-linking and halogen bond effect simultaneously in this cross-linked network, halogen key is made The degree of cross linking being crosslinked with provided supermolecular mechanism is in its gel point above and below.

19. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and acted on simultaneously containing covalent cross-linking and cation-π in this cross-linked network, sun Ion-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.

20. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and acted on simultaneously containing covalent cross-linking and anion-π in this cross-linked network, sun Ion-π acts on the degree of cross linking of provided supermolecular mechanism crosslinking in its gel point above and below.

21. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the hybrid cross-linked dynamic is poly- It closes object and only contains a cross-linked network, and contain covalent cross-linking and radical cation dimerization simultaneously in this cross-linked network It acts on, the degree of cross linking of the crosslinking of supermolecular mechanism provided by radical cation dimerization is in its gel point above and below.

22. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that constitute the formula of dynamic aggregation object Component further include it is following any or appoint it is several can additive: other polymers, auxiliary agent, filler；

Wherein, addible other polymers be selected from it is following any or appoint it is several: natural polymer, synthetic resin, Synthetic rubber, synthetic fibers；

Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, dispersion Agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；

Wherein, addible filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler.

23. according to claim 1 to hybrid cross-linked dynamic aggregation object described in any one of 22, which is characterized in that described is dynamic The form of state polymer or its composition has following any: gel, ordinary solid, elastomer, foamed material.

24. according to claim 1 to hybrid cross-linked dynamic aggregation object described in any one of 22, which is characterized in that it is applied to Self-repairability material, sealing material, toughness material, adhesive, toy material, stationery material and shape memory material, force snesor Material, energy storage device material.