CN109422836A - A kind of dynamic crosslinking polymer containing combination supermolecular mechanism - Google Patents

A kind of dynamic crosslinking polymer containing combination supermolecular mechanism Download PDF

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CN109422836A
CN109422836A CN201710523816.6A CN201710523816A CN109422836A CN 109422836 A CN109422836 A CN 109422836A CN 201710523816 A CN201710523816 A CN 201710523816A CN 109422836 A CN109422836 A CN 109422836A
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effect
polymer
dynamic crosslinking
supermolecular
crosslinking polymer
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不公告发明人
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Xiamen Tiance Material Technology Co ltd
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Weng Qiumei
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    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract

A kind of dynamic crosslinking polymer containing combination supermolecular mechanism, its degree of cross linking for containing at least two supermolecular mechanisms and at least one supermolecular mechanism is more than the gel point of its crosslinking, based on wherein at least one-object effect, the dynamic crosslinking polymer has the supermolecular mechanism of Different Dynamic by introducing, and can prepare that invertibity is strong, polymer material of structure-rich, performance multiplicity.Possessed otherness between supermolecular mechanism not of the same race in dynamic crosslinking polymer, so that polymer reflects the dynamic reversible effect with hierarchy, which can be used as self-repair material, toughness material, sealing material, force snesor material etc. and is widely applied.

Description

A kind of dynamic crosslinking polymer containing combination supermolecular mechanism
Technical field:
The present invention relates to intelligent polymer fields, and in particular to a kind of dynamic crosslinking polymerization containing combination supermolecular mechanism Object.
Background technique:
Supramolecular chemistry is the chemistry that molecule aggregate is formed based on intermolecular non-covalent interaction, is mainly ground Study carefully the weak interaction of the non-covalent bond between molecule and the synergistic effect between them and the assembling of the molecule aggregate that generates, Structure and function.Supermolecule polymer is a uncharted field in polymer science research, based on the weak of supramolecular chemistry It interacts and there is dynamic reversibility, be a kind of completely new intellectual material.The active force of supermolecular mechanism is smaller, required for Dynamic condition it is also relatively mild, dynamic property is preferable, is constructing functional molecular and material, exploitation chemical sensor, regulation biology Molecule, control smart molecule switch and machine etc. show important function.
The supermolecular mechanism type found at present is more and more abundant, for being formed by dynamic crosslinking by supermolecular mechanism The report of polymer is also more and more, is concentrated mainly in every kind of dynamic crosslinking polymer and contains only a kind of supermolecular mechanism to mention For the dynamic of polymer, but since the dynamic property of single supermolecular mechanism is limited, it is difficult to be formed and cooperate with orthogonal synthesis Performance.
As the use scope of dynamic crosslinking polymer is more and more extensive, obtained dynamic crosslinking polymer is specific Dynamic is lost in environment sometimes, in order to obtain with diversity and cooperate with orthogonal dynamic, and in various environment The dynamic crosslinking polymer that can be stabilized needs to develop a kind of new supermolecular mechanism compositional model, to solve existing dynamic Deficiency present in cross-linked polymer.
Summary of the invention:
The present invention is directed to above-mentioned background, provides a kind of dynamic crosslinking polymer containing combination supermolecular mechanism, described Dynamic crosslinking polymer contain the degree of cross linking of at least two supermolecular mechanisms and at least one supermolecular mechanism in its crosslinking More than gel point, wherein the supermolecular mechanism is at least selected from Host-guest effect, ionization, close metal function, idol Pole-dipole effect, halogen bond effect, cation-π effect, anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, hydrogen bond are made With, metal-ligand effect, ion hydrogen bond action, radical cation dimerization, based on wherein at least one-object makees With, and at least one Host-guest effect based on selected from ether, ring is luxuriant, Cucurbituril, calixarenes, column aromatic hydrocarbons and inorganic The combined main body of organic ion skeleton.
Polymer chain topological structure in the dynamic crosslinking polymer and its composition and material composition is selected from line style, ring Shape, branching, cluster, crosslinking and combinations thereof form.
A preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain At least two supermolecular mechanisms and wherein at least one are that the Host-guest acts on, wherein the supermolecule of all kinds is made The degree of cross linking is more than gel point.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein at least one supermolecule is made The degree of cross linking is more than gel point, and the degree of cross linking of at least one supermolecular mechanism is below gel point.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein the supermolecule of all kinds The degree of cross linking in gel point hereinafter, but the sum of its degree of cross linking more than gel point.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein Host-guest effect The degree of cross linking is more than gel point, and the sum of degree of cross linking of remaining supermolecular mechanism is below gel point.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein all Host-guests are made The sum of degree of cross linking is in gel point hereinafter, the sum of degree of cross linking of remaining supermolecular mechanism is more than gel point.
In embodiments of the present invention, Host-guest effect comprising host molecule (being indicated with H) and visitor The various combination of body molecule (being indicated with G), the host molecule include but are not limited to ether (including crown ether, cave ether, ball ether, Hemisphere ether, pod-like ether, lasso trick ether, benzo-crown ether, miscellaneous crown ether, miscellaneous cave ether, mixing cave ether), ring is luxuriant, Cucurbituril, calixarenes, column virtue Hydrocarbon and suitable inorganic organic ion skeleton, at least one Host-guest effect based on selected from ether, ring is luxuriant, cucurbit The combination of the main body of urea, calixarenes, column aromatic hydrocarbons and suitable inorganic organic ion skeleton.The guest molecule includes but not It is only limitted to suitable long chain alkane, cycloalkane, heterocycloalkane, aromatic hydrocarbons, heteroaryl hydrocarbon, condensed cyclic structure compound, heterocycle structure chemical combination Object, single ring architecture compound, multiring structure compound, spirane structure compound, caged scaffold compound, suitable ion cluster.
In embodiments of the present invention, the ionization refers at least containing in dynamic crosslinking polymer architecture There is the ionic group of a pair of of oppositely charged, ionization is formed by Coulomb force between cation group and anion group.
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, 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 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 described π-π stacking effect refers in dynamic crosslinking polymer containing can The structure of pi bond electron cloud is provided, is acted on by the mutual overlapping π-π stacking that formed of pi bond electron cloud.
In embodiments of the present invention, the hydrogen bond action, by being present in dynamic crosslinking polymer chain skeleton (packet Include 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.It is described Hydrogen bond group preferably comprise following constituent:
At least one of further preferably 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-LxIt 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 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, the form of the dynamic crosslinking polymer can be solution, lotion, cream, glue, general Logical solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid Swell gel), foamed material etc..
In embodiments of the present invention, a kind of dynamic crosslinking polymer containing combination supermolecular mechanism, constitutes dynamic The raw material components of polymer 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 dynamic crosslinking polymer containing combination supermolecular mechanism described in embodiments of the present invention, application In following product: force snesor material, self-repairability coating, self-repairability plate, self-repairability binder, toughness material, shape Shape memory material, sealing material, energy storage device material, toy material, stationery material.
Compared with prior art, the invention has the following advantages:
(1) in dynamic crosslinking polymer of the invention, host molecule and guest molecule stable in the polymer can be deposited , formed Host-guest action intensity it is moderate, can interact or dissociate under the conditions of relatively mild, make dynamically hand over The dynamic of linked polymer will be achieved under ordinary conditions.Host-guest based on ethers main body is acted on for organic The complexing power of cation has unique advantage；Host-guest based on the luxuriant human subject of ring acts on MOLECULE DESIGN or molecule machine There is property in the building of device；Host-guest effect based on calixarene kind main body has the complexing of guest molecule Stronger adaptability and selectivity, whether neutral object or ion object, whether aqueous phase system or oil-based system, It can be very good to be acted on；Host-guest effect based on Cucurbituril human subject, different Cucurbituril main bodys can be selective Various sizes of guest molecule is complexed in ground；Based on column aromatic hydrocarbons human subject Host-guest effect, the high degree of symmetry of column aromatic hydrocarbons and just Property structure make it that there is excellent complexing power to guest molecule, while column aromatic hydrocarbons can be regulated and controled by the derivatization of column aromatic hydrocarbons Host-guest property, keep its scope of application wider.
(2) in dynamic crosslinking polymer of the invention, on the basis of containing Host-guest effect, along with others Supermolecular mechanism can obtain a wide range of adjustable performance such as intensity, dynamic and responsiveness；Meanwhile these supermolecular mechanisms Time sequence fracture can be carried out in the form of " key can be sacrificed " under external force, it is tough to provide excellent stretching for cross-linked polymer Property and tear resistance；On the other hand super stretching percentage of elongation can be obtained；In addition, the intensity of different types of supermolecular mechanism, Structure, dynamic, responsiveness and formation condition etc. are different, can achieve collaboration and the orthogonal impact of performance, make material Structure and performance have more adjustability.The present invention will carry out sufficient utilization and combination the advantages of various supermolecular mechanisms, make State polymer remove the dynamic generally having with usual supermolecular mechanism polymer, self-repairability, repeat processability with Outside, there is also various other performances: such as the directionality of halogen bond effect, cation-π effect, anion-π effect, Host-guest To small molecule/controllable selectivity of ion/group and controllable identity in effect, what benzene-fluorobenzene effect, π-π stacking acted on has Sequence, ionization (negative ions are to effect), the pH of ion hydrogen bond action, concentration sensitive, electric conductivity, close metal phase interaction The characteristics such as the special photo electric with, radical cation dimerization, can according to demand reasonable selection supermolecular mechanism group/ Unit carries out MOLECULE DESIGN.
(3) dynamic effect of supermolecular mechanism is good in dynamic crosslinking polymer, dynamic condition is mild.Compared to existing Other dynamic covalent systems, the present invention take full advantage of supermolecular mechanism with good chemical stability and high dynamic can Inverse property, can without catalyst, without high temperature, illumination or specific pH under conditions of realize the synthesis of dynamic crosslinking polymer and dynamic State invertibity also reduces the limitation of use environment while improving preparation efficiency, and extend polymer applies model It encloses.
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 dynamic crosslinking polymer containing combination supermolecular mechanism, contain at least two supermolecules The degree of cross linking of effect and at least one supermolecular mechanism is more than the gel point of its crosslinking, wherein the supermolecular mechanism is extremely Acted on less selected from Host-guest effect, ionization, close metal function, dipole-dipole effect, halogen bond effect, cation-π, Anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, hydrogen bond, metal-ligand effect, ion hydrogen bond action, free radical sun Ion dimerization, based on wherein at least one-object effect, and at least one Host-guest effect is based on choosing From ether, ring is luxuriant, combined main body of Cucurbituril, calixarenes, column aromatic hydrocarbons and inorganic organic ion skeleton.Dynamic crosslinking polymer In the supermolecular mechanism that contains once dissociating, polymeric system is decomposed into following any or appoints several secondary units: poly- Close object chain segment, polymer cluster etc.；Meanwhile the phase of supermolecular mechanism can be passed through between dynamic crosslinking polymer and said units Interaction is mutually converted with dissociation realization and dynamic reversible.
Term " polymerization " reaction/action used refers to the reactant of lower molecular weight if not otherwise indicated in the present invention By the reaction formations such as polycondensation, addition polymerization, ring-opening polymerisation formed have higher molecular weight product process, i.e., except crosslinked action with Propagation process/effect of outer chain.Wherein, reactant can for polymerizing power (can spontaneously be polymerize, or Can be in initiator or outer plus be polymerize under capable of acting on) the compounds such as monomer, oligomer, prepolymer.By a kind of reactant The product being polymerize is known as homopolymer.It should be pointed out that " polymerization " in the present invention comprising except reaction Linear growth process, branching process, annulation process of reactant molecule chain other than object strand cross-linking process etc.；In the present invention Embodiment in, " polymerization " includes the chain as caused by the bonding of covalent bond and the noncovalent interaction of supermolecular mechanism Propagation process.
Term " crosslinking " reaction/action used in the present invention, if not otherwise indicated, refer between reactant molecule and/or The process with three-dimensional unlimited reticular pattern product is formed in reactant molecule by the physical action of supermolecular mechanism.It had been crosslinked Cheng Zhong, polymer chain is general first to be increased in two-dimensional/three-dimensional direction, gradually forms two dimension or three-dimensional cluster, developing deeply three Tie up infinite network structure.It should be noted that the cross-linked structure in the present invention, refer in particular to gel point or more (containing gel point, under Three-dimensional infinite network structure together), and non-crosslinking structure then refers to the structures such as line style, ring-type, branching and gel point or less Two dimension, three-dimensional cluster structure.Heretofore described " gel point " (also referred to as percolation threshold), refers to that reactant is being crosslinked In the process, viscosity is uprushed, and starts gel phenomenon occur, starts reaction when crosslinking reaches a three-dimensional infinite network for the first time Point.Cross-linking products more than gel point (containing gel point), have three-dimensional infinite network structure, and cross-linked network constitutes one Integrally and across entire polymer architecture, cross-linked structure is relatively stable and secured；In gel point cross-linking products below, not Three-dimensional infinite network structure is formed, a small amount of two dimension or three-dimensional net structure only is being locally present, and is not belonging to across entire poly- Close the cross-linked network that can constitute an entirety of object structure.In this patent, if not otherwise specified, the crosslinking is equal Refer in particular to supermolecular mechanism crosslinking
The dynamic crosslinking polymer, polymer chain topological structure be selected from line style, ring-type, branching, cluster, crosslinking and A combination thereof form；It is formed and the chain topological structure of the polymer in raw material also can be selected from line style, ring-type, branching, cluster, crosslinking And combinations thereof form.When containing multiple compositions, can be mutually blended between difference composition, is mutually interspersed, can be dissolve each other or It is immiscible.
Wherein, described " line style " structure, refer to polymer molecular chain presentation is rule or irregular long chain line Shape is generally formed by connecting on a continuous length by many repetitive units, and the side group in polymer molecular chain is not generally with branch Chain exists；It is usually that polycondensation reaction, sudden reaction or open loop are passed through by the monomer without long-chain side group for " linear structure " The polymerizations such as reaction are formed.
Wherein, described " ring-type " structure, refers to that polymer molecular chain exists in the form of closed chain comprising single The cyclic structure of the forms such as ring, polycyclic, bridged ring, nested rings；For " cyclic structure ", line style or branched polymer can be passed through Intramolecular and/or it is intermolecular cyclization formed, can also pass through ring expansion polymerization react the methods of preparation.
Wherein, described " branching " structure refers on polymer molecular chain containing the knot such as side chain, branch and bifurcated chain Structure includes but are not limited to the structures such as star-like, H-type, combed, dendritic, hyperbranched and combinations thereof and itself and line style, ring-type Structure is further combined, such as line style chain end connection ring shape structure, and cyclic structure is in conjunction with comb-type structure, dendritic last-in-chain(LIC) End connection endless chain, etc.；For " structures such as side chain, branch and bifurcated chain of polymer ", there can be multilevel structure, such as It can continue to have one or more levels branch on the branch of polymer molecular chain.For " branched structure ", preparation method is all It is more, it is generally well known to those skilled in the art, such as polycondensation reaction can be carried out by the monomer containing long-chain side group and be formed, Perhaps the chain transfer reaction in addition polymerization process through free radical is formed or by radiation and chemical reaction in line style strand On extend branched structure and formed.Branched structure further progress intramolecular and/or intermolecular reaction (crosslinking) can produce Cluster and cross-linked structure.
Wherein, described " cluster " structure refers to that polymer chain carries out intramolecular and/or intermolecular reaction and generates Gel point two-dimensional/three-dimensional structure below.
Wherein, described " crosslinking " structure, spy refer to the three-dimensional infinite network structure that polymer has.
It in embodiments of the present invention, can be only in the dynamic crosslinking polymer and its composition and material composition There is a kind of polymer of topographic morphologies, is also possible to the mixture of the polymer there are many topographic morphologies.
In embodiments of the present invention, supermolecular mechanism by any suitable location in dynamic crosslinking polymer include but It is not limited only to polymer backbone, side group, the supermolecular mechanism group in end group/unit interaction and realizes.And any position Supermolecular mechanism in chain, supermolecule in such chain can be formed under certain condition between the supermolecular mechanism group/unit set Effect does not generate crosslinked action directly, but if generating nested rings can then crosslink.
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 according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain At least two supermolecular mechanisms and wherein at least one are that the Host-guest acts on, wherein the supermolecule of all kinds is made The degree of cross linking is more than gel point.In the embodiment, the degree of cross linking of dynamic crosslinking polymer is high, facilitates and obtains high mechanics The intensity effect orthogonal with cooperateing with.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein at least one supermolecule is made The degree of cross linking is more than gel point, and the degree of cross linking of at least one supermolecular mechanism is below gel point.In the embodiment, until Supermolecular mechanism based on rare one kind, also the supermolecular mechanism at least supplemented by one kind, facilitates and carries out small range regulation.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein the supermolecule of all kinds The degree of cross linking in gel point hereinafter, but the sum of its degree of cross linking more than gel point.It, can be to the maximum extent in the embodiment Utilize each supermolecular mechanism.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein the Host-guest The degree of cross linking of effect is more than gel point, and the sum of degree of cross linking of remaining supermolecular mechanism is below gel point.The embodiment In, the Host-guest effect is supplemented with other supermolecules.
Another preferred embodiment according to the present invention, the dynamic crosslinking polymer have cross-linked structure, contain There are at least two supermolecular mechanisms and wherein at least one is that the Host-guest acts on, wherein all main bodys- The sum of degree of cross linking of object effect is in gel point hereinafter, the sum of degree of cross linking of remaining supermolecular mechanism is more than gel point.The reality It applies in mode, the Host-guest is used as the supplement of other supermolecular mechanisms.
The present invention can also have other embodiments, and those skilled in the art can be with logic according to the present invention and train of thought Reasonably realize.
In dynamic crosslinking polymer of the invention, host molecule and guest molecule can stable presence in the polymer, The Host-guest action intensity that it is formed is moderate, can interact or dissociate under the conditions of relatively mild, keeps dynamic crosslinking poly- The dynamic for closing object will be achieved under ordinary conditions.
In embodiments of the present invention, various supermolecular mechanisms may be in same polymer chain/network structure, It can be independently of each other in different polymer chain/network structures.
Above-mentioned supermolecular mechanism is mutually indepedent, refers to that the supermolecular mechanism is in different non-friendships each independently In linked polymer chain or in different crosslinking polymer networks, mutually it is blended between the crosslinking and/or non-cross-linked polymer of formation Or it is mutually interspersed.Constituted dynamic crosslinking polymer, the dynamic between component are formed using mutually independent polymer Property can be collocated with each other, independent effect, to embody better toughness and selfreparing effect.
In embodiments of the present invention, Host-guest effect comprising host molecule (being indicated with H) and visitor The various combination of body molecule (being indicated with G), the host molecule include but are not limited to ether (including crown ether, cave ether, ball ether, Hemisphere ether, pod-like ether, lasso trick ether, benzo-crown ether, miscellaneous crown ether, miscellaneous cave ether, mixing cave ether), ring is luxuriant, Cucurbituril, calixarenes, column virtue Hydrocarbon and suitable inorganic organic ion skeleton, at least one Host-guest effect based on selected from ether, ring is luxuriant, cucurbit The combination of the main body of urea, calixarenes, column aromatic hydrocarbons and suitable inorganic organic ion skeleton, preferably crown ether, benzo-crown ether, cave Ether, cucurbit [8] urea, cup [4] aromatic hydrocarbons, column [5] aromatic hydrocarbons.The guest molecule include but are not limited to suitable long chain alkane, It is cycloalkane, heterocycloalkane, aromatic hydrocarbons, heteroaryl hydrocarbon, condensed cyclic structure compound, heterocycle structure compound, single ring architecture compound, polycyclic Structural compounds, spirane structure compound, caged scaffold compound, suitable ion cluster, preferably long chain alkane, heterocyclic compound Object, polycyclic compound, endocyclic compound, suitable ion cluster.Host molecule and guest molecule can be stable in the polymer In the presence of the Host-guest action intensity formed is moderate, can interact or dissociate under the conditions of relatively mild, makes dynamic The dynamic of polymer will be achieved under ordinary conditions；One host molecule can identify the multiple guest molecules of bonding, In embodiments of the present invention, a preferably host molecule at most interacts with two guest molecules.
Suitable main group can be exemplified below, but the present invention is not limited only to this:
Ni(PDC)(H2O)2Skeleton, Zn3(PTC)2(H2O)8·4H2O skeleton；
Suitable guest moieties can be exemplified below, but the present invention is not limited only to this:
In embodiments of the present invention, preferred Host-guest effect can be selected from following combination, but the present invention not only limits In this:
In embodiments of the present invention, the ionization refers at least containing in dynamic crosslinking polymer architecture There is the ionic group of a pair of of oppositely charged, ionization is formed by Coulomb force between cation group and anion group.Institute The cation group stated is a kind of organic group for being easier to receive proton, by way of example, it is included but are not limited to: It is preferred thatThe anion group is that one kind is easier to lose The organic group of deprotonation, by way of example, it is included but are not limited to:It is preferred thatUnder particular case, cation group and anion group be may be in the same compound structure, such as The compounds such as choline glycerophosphate, 2- methacryloxyethyl phosphocholine, L-carnitine.Ionization can stablize Ground is present in polymer, and concentration and type by changing ionic group, can carry out very to the strong and weak of ionization Good control.
In embodiments of the present invention, there is no particular restriction for the combination of cation group and anion group, as long as just Ionic group can form suitable ionization with anion group.Some suitable combinations can be exemplified below, but The present invention is not limited only to this:
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, 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=O, C-F, H-O, more It is preferred that C ≡ N.Dipole-dipole effect can be stable be present in polymer, be easy to regulate and control, the pairing for acting on group can To generate microdomai pi, make to interact more stable；When temperature is higher, dipole-dipole effect, which can weaken, even to disappear, therefore contains The polymer for having dipole-dipole to act on 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 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 crosslinking polymer 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 crosslinking Stable halogen bond effect is formed in polymer.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 crosslinking polymer 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 can hand in dynamic Stable cation-π effect is formed in linked polymer.Some suitable cation groups can be exemplified below, but this hair It is bright to be 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 crosslinking polymer 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 crosslinking polymer.Some suitable anion can be exemplified below, but this Invention 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 crosslinking polymer of specific function.
In embodiments of the present invention, benzene-fluorobenzene effect type is not restricted, as long as long as can hand in dynamic Stable benzene-fluorobenzene effect is formed in linked polymer.Some suitable benzene-fluorobenzene effect can be exemplified below, but this hair It is bright to be not limited only to this:
In embodiments of the present invention, the described π-π stacking effect refers in dynamic crosslinking polymer containing can The structure of pi bond electron cloud is provided, is acted on by the mutual overlapping π-π stacking that formed of pi bond electron cloud.The mode of action that π-π is stacked There are three types of, including the accumulation of face face, offset accumulation and the accumulation of side face.Wherein, face face accumulation refers to the anchor ring of interaction each other In parallel, and the distance at parallel anchor ring center and the distance between anchor ring are almost equal, and the π-π effect of this accumulation mode is electrostatic Mutual exclusion, it is more unstable, but when the substituent group connected on anchor ring is electron-withdrawing stronger, the π-π of face face accumulation, which is acted on, to be become It obtains obvious；Offset accumulation refers to that effect anchor ring is parallel to each other, but there is certain deviation at ring center, i.e. the distance at ring center is big In ring distance between the surface, this accumulation mode alleviates the mutual repulsion effect between two anchor rings, has increase accordingly the attraction of σ-π, It is relatively common accumulation mode；Accumulation mode other than accumulating in addition to face face and deviating accumulation is known as the accumulation of side face, this heap Product mode energy is minimum, and intermolecular repulsion is minimum, is common between the lesser Circlewise conjugated molecule in Van der Waals surface or flexible company Between the Circlewise conjugated molecule for connecing son.
It is capable of providing the compound structure of pi bond electron cloud, including but not limited to most fused ring compound and some is deposited In the pi-conjugated heterocyclic compound of π-, suitable group can be exemplified below, but the present invention is not limited only to this:
It is preferred thatπ-π is stacked It is simple to act on generation type, can be stable in the presence of in polymer, influenced by external environment it is smaller, can be convenient by changing Become conjugated compound and content regulates and controls it.
In embodiments of the present invention, providing the combination of the compound of pi bond electron cloud, there is no particular restriction, as long as chemical combination Suitable π-π stacking effect is formed between object.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 oversubscription Ring formation exists in son polymerization and/or crosslinking and/or chain namely hydrogen bond can be played only and connect two or more segments 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 bond Play 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 crosslinking polymer to keep balanced structure and raising mechanical property (modulus and intensity).If the tooth of hydrogen bond Number is few, then intensity is low, and the dynamic of hydrogen bond action is with regard to strong.In embodiments of the present invention, the preferably more than hydrogen bond of four teeth Effect.
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:
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 containing that can contain in one or more kinds of hydrogen bond group namely dynamic crosslinking polymer in cross-linked network Or the combination of a variety of hydrogen bond groups.The hydrogen bond group can be formed, example by the reaction between any appropriate group Such as: passing through the covalent reaction shape between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups and amino At；It is formed by the covalent reaction between isocyanate groups and hydroxyl, sulfydryl, carboxyl；Pass through succinimide group and ammonia Base, hydroxyl, the covalent reaction between sulfydryl are formed.
In the present invention, the hydrogen bond action, which can be, carries out the process of dynamic supermolecule crosslinking in dynamic crosslinking polymer Middle generation；Dynamic supermolecule crosslinking is carried out again after being also possible to pre-generated hydrogen bond action；It can also be crosslinked in dynamic supermolecule After formation, hydrogen bond action is generated during dynamic crosslinking polymer subsequent forming, but the present invention is not limited only to this.
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-LxIt 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.
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 in a polymer chain or a dynamic crosslinking polymeric system Kind ligand, can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand refers to that a kind of core is matched Body structure, a framework counterpart, pendant ligands, end group ligand can have same core ligand structure, their difference It is in and accesses the tie point and/or position difference of polymer chain or small molecule in core ligand structure.Suitable ligand combination The dynamic crosslinking polymer with particular characteristic can be effectivelyed prepared, such as plays collaboration and/or orthogonal effect, promotes material The comprehensive performance of material.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 in dynamic crosslinking polymeric system When molecular compound, the core ligand structure can also be at the polymer of the non-covalent or the end of small molecule compound End is used as 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 forms 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 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 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, 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 groups, and the composition of metal-ligand effect can be formerly formed with ligand Polymerized/cross-linked is carried out again, can also be re-introduced into after completing polymerized/cross-linked.It is preferred that being introduced after generating ligand groups.
In embodiments of the present invention, preferred supermolecular mechanism combination includes but are not limited to combine as follows:
Host-guest effect and hydrogen bond action, two kinds of supermolecular mechanism generation types are simple and can be stabilized, made The dynamic crosslinking polymer obtained has good toughness and self-healing properties；Host-guest effect and metal-ligand effect, benefit The recognition reaction acted on two kinds can be such that the specific Function of dynamic crosslinking polymer greatly improves；Host-guest effect and Ionization, ionic group in this dynamic crosslinking polymer have certain electric conductivity, prepare fexible conductor and There is special advantage in energy storage device material；Host-guest effect and dipole-dipole effect, increased dipole-dipole effect The mechanical property of dynamic crosslinking polymer can further be promoted；Host-guest effect and the effect of π-π stacking, Host-guest effect Guest molecule be much also capable of forming π-π stacking effect, therefore this supermolecular mechanism combination prepare it is relatively simple； Host-guest effect and metal-ligand effect and hydrogen bond action, the active force of these three supermolecular mechanisms is all relatively stable, system The dynamic crosslinking polymer stabilisation and mechanical property obtained is more preferable, and it can be made up by hydrogen bond action in flexibility It is insufficient；Host-guest effect and metal-ligand effect and the effect of π-π stacking, the effect group letter of these three supermolecular mechanisms It is single, only need a guest moieties and main group and corresponding metal ion that can be formed simultaneously these three supermolecules sometimes The dynamic crosslinking polymer of effect, this supermolecular mechanism combination usually has preferable mechanical stability and functional characteristic.
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, C1-4Alkyl, 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 nested ring structure being previously mentioned refers in cyclic structure containing connected or embedding to each other by two or more rings The cyclic structure constituted is covered, is illustrated 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 crosslinking polymer or its composition can be solution, cream Liquid, cream, glue, ordinary solid, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ion Liquid swell gel), elastomer, foamed material etc., wherein the dissolvable small-molecular-weight contained in ordinary solid and foamed material Component content is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Solution There is good mobility with lotion, shear thickening effect can be fully demonstrated in a fluid, while can also be used what it had Coating carrys out prepares coating.Cream is usually concentrated emulsions, and glue is usually the polymer of concentrated solution or lower glass transition temperatures, energy Enough embody good plasticity and fillable.The shape and volume of ordinary solid are relatively more fixed, have preferably mechanical strong Degree, can not be by the constraint of organic sweller or water.Elastomer has the general properties of ordinary solid, but has simultaneously preferable Elasticity, and it is softer.Gel then has good flexibility, can embody preferable resilience, preferably by plasticizer, The gel of ionic liquid, oligomer and boiling point the organic solvent swelling higher than water.Foamed material then has density low, light excellent The mechanical strength of point, the brittleness and organogel that can also overcome the problems, such as part ordinary solid is relatively low, and soft foam material also has 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 crosslinking polymer gel can be by sweller (including water, You Jirong One of agent, oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also be in dynamic crosslinking polymer Sweller is recycled to carry out swelling acquisition after the completion of preparation.Certainly, the present invention not only limit and this, those skilled in the art can root According to logic and train of thought of the invention, rationally and effectively realize.
In the preparation process of dynamic crosslinking polymer, mechanical foaming method, physical blowing method, chemical blowing process are mainly used Three kinds of methods foam to dynamic crosslinking polymer.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic crosslinking polymer big Amount air or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through Physically or chemically variation is allowed to be molded with as foamed material.Air and addition emulsifier or table can be passed through to shorten molding cycle Face activating agent.
Wherein, the physical blowing method is using physical principle in the preparation process of dynamic crosslinking polymer come real The foaming of existing polymer comprising but it is not limited only to following methods: (1) inert gas blown method, i.e., lazy under pressurized condition Property gas indentation molten polymer or pasty material in, then decompression heating, make dissolution gas expansion and foam；(2) it utilizes Low-boiling point liquid evaporation gasification foaming makes that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime Liquid dissolves in polymer (particle), then heats and softens polymer, and liquid also gasifies therewith evaporation and foamed；(3) it dissolves out Method is immersed in polymer with liquid medium and dissolves added solid matter in advance, makes occur a large amount of holes in polymer And in foaming shape, such as by solable matter salt elder generation and mixed with polymers, water is placed on after being shaped to product, then by product In handle repeatedly, solable matter dissolve out to get arrive open-celled foam product；(4) hollow microsphere method is added in the material It is combined after hollow microsphere as obturator-type foamed polymer；(5) expandable particles method is filled, expandable of first mixing filling Grain makes expandable particles foam in molding or mixed process with the polymer material of activity foaming；Wherein, preferably by poly- Inert gas is dissolved in conjunction object and the method for low-boiling point liquid foams.Using physical blowing method, have operation Poisoning compared with The advantages that small, cost is relatively low for foaming raw material, foaming agent noresidue body.Further, it is also possible to be prepared using freeze-drying.
Wherein, the chemical blowing process is to generate during dynamic crosslinking polymer foaming along with chemical reaction Gas and the method to foam comprising but it is not limited only to following two method: (1) thermal decomposable foaming agent foaming utilizes The gas decomposed to give off after chemical foaming agent heating foams.(2) it interacts between polymers compositions and generates the foaming of gas Method generates inert gas (such as carbon dioxide that is, using the chemical reaction occurred between two or more components in foaming system Or nitrogen) polymer is caused to expand and foam.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to protect Card product has preferable quality, and a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by The method for adding chemical foaming agent in the polymer foams.
In the preparation process of dynamic crosslinking polymer, is mainly formed using moulded from foam, is injection-expansion molded and crowded Three kinds of methods of foaming form dynamic crosslinking polymer foams out.
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 making foam solidifying and setting 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.It is more more competitive than injection-expansion molded since it can not only realize continuous production, and in cost, because This is current most widely used foaming technology.
In the preparation process of dynamic crosslinking polymer, those skilled in the art can be according to practical preparation situation and mesh Mark polymer performance select suitable foaming method and foamed material forming method to dynamic crosslinking polymer foams into Row preparation.
In embodiments of the present invention, the structure of dynamic crosslinking polymer foams is related to open-celled structure, closed pore knot Structure, three kinds of half-open semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional are all It can be that 0.01-3mm is differed by gas or liquid, abscess diameter.Hole-closing structure has individual blisters structure, inner cell and bubble There is wall film to separate between hole, the overwhelming majority is not interconnected, and abscess diameter is that 0.01-3mm is differed.The existing phase of contained abscess It is intercommunicated and to have mutual disconnected structure be then half open-celled structure.It, can also be by machinery for having formed the foaming structure of closed pore Pressure or chemical method become open-celled structure, and those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic crosslinking polymer foams are according to its softness, can be divided into it is soft, Hard and 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 crosslinking polymer foams can be divided into again according to its density low ratio foamed, Middle foaming 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 bubble of middle foaming Foam 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 other polymers, auxiliary agent, filler, sweller 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.
Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, It can be selected from natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and is had Some molecular weight can be oligomer or high polymer according to the difference of molecular weight, not according to polymeric species without limitation Together, can be homopolymer, in the specific use process should according to the performance of target material and the needs of actual fabrication process and It 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 Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, polyimides, polyacrylate, polypropylene Nitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact polystyrene, polysulfones, polytetrafluoroethylene (PTFE), poly- ammonia Ester, polyvinyl acetate, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), gathers polyureas Isoprene, poly- (the chloro- 1,3- butadiene of 2-), dimethyl silicone polymer, Polymethyl methacrylate, gathers poly- suitable butadiene Methyl phenyl siloxane, poly- methyl vinyl phenyl siloxanes, poly- methyl ethylene trifluoropropyl siloxane, Hydrin Deng.
In the preparation process of dynamic crosslinking polymer 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.Institute The addible auxiliary agent stated is selected from following any or several auxiliary agents: additive synthesis, including catalyst, initiator；It stabilizes Auxiliary agent, including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve processing performance Auxiliary agent, including lubricant, release agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent；Change surface property Auxiliary agent, including antistatic agent, emulsifier, dispersing agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustring Agent；Fire retardantization 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, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used 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: chlorinated polyethylene resin (CPE), poly- suitable fourth Diene, polyvinyl alcohol etc..Wherein, the preferred chlorinated polyethylene resin of toughener (CPE), toughener dosage used do not limit especially It is fixed, 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 C5~9Sour glycol ester, C5~9Sour 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, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified alkalinity are inflatable newborn Liquid (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1 wt%.
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, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, gathers at colloidal aluminum Acrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc..Wherein, the preferred coconut palm of thickener Seed oil diglycollic amide, thickener dosage used are 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, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, two boronations Titanium 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, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, enzyme, hormone, raw lacquer, wood powder, shell powder, wood Sugar, 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 crosslinking polymer material, the preferred antioxidant of addible auxiliary agent, light stabilizer, heat are steady Determine agent, toughener, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of addible filler, barium sulfate, talcum powder, carbon black, glass Glass microballon, graphene, glass fibre, carbon fiber.
In the preparation process of dynamic crosslinking polymer, the additive amount of dynamic crosslinking polymer 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.
In the preparation process of hydridization dynamic crosslinking polymer, it can be mixed by any appropriate material known in the art The raw material centainly matched is prepared dynamic crosslinking polymer by mixing by mode, can be interval, semicontinuous or continuous work The mixing of skill form；Similarly, also may be selected interval, semicontinuous or continuous processing form to dynamic crosslinking polymer carry out at Type.The hybrid mode of use include but are not limited to solution be stirred, melt be stirred, mediate, mixing, mill, melting Extrusion, ball milling etc., wherein it is preferred that solution is stirred, melts and be stirred and melting extrusion.Energy in material mixed process Amount offer form includes but are not limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to Extrusion molding, injection moulding, compression molding, tape casting, calendering formation, cast molding.
The specific method of preparation hydridization dynamic crosslinking polymer is stirred using solution, usually by raw material to dissolve or The form of dispersion is stirred mixing in the reactor in respective solvent or in common solvent.In general, hybrid reaction Temperature is controlled at 0-200 DEG C, and preferably 25-120 DEG C, more preferable 25-80 DEG C, mixing time is controlled in 0.5-12h, preferably 1- 4h.The product obtained after mixing can be poured into suitable mold, at 0-150 DEG C, preferably 25-80 DEG C of temperature condition Under, 0-48h is placed, polymer samples are obtained.
Used solvent, should carry out according to actual conditions such as reactant, product and reaction process in above-mentioned preparation method Selection includes but are not limited to following any solvent or appoints the mixed solvent of several solvents: deionized water, acetonitrile, acetone, fourth Ketone, benzene,toluene,xylene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, chloroform, methylene chloride, 1,2- dichloro The positive fourth of ethane, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, isopropyl acetate, acetic acid Ester, trichloro ethylene, mesitylene, dioxanes, Tris buffer, citrate buffer solution, acetic acid buffer solution, phosphate buffer solution Deng；It is preferred that deionized water, toluene, chloroform, methylene chloride, 1,2- dichloroethanes, tetrahydrofuran, dimethylformamide, phosphoric acid are slow Rush solution.In addition, solvent is also selected from oligomer, plasticizer, ionic liquid；The oligomer includes but are not limited to poly-vinegar Vinyl acetate oligomer, polyacrylic acid N-butyl oligomer, atoleine etc.；The plasticizer can be selected from addible auxiliary agent In plasticizer described in classification, which is not described herein again；The ionic liquid is generally by organic cation and inorganic anion Composition, cation are usually that see imidazol ion, N- alkyl that ion, 1,3- dialkyl group replace of alkyl quaternary ammonium ion, alkyl quaternary takes The pyridinium ion etc. in generation；Anion is usually halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, also has CF3SO3 -、 (CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、 (C2F5SO2)2N-、SbF6 -、 AsF6 -Deng.Wherein, when preparing dynamic crosslinking polymer using deionized water and selecting to be retained, available hydrogel； When preparing dynamic crosslinking polymer using organic solvent and selecting to be retained, available organogel；Utilize oligomer Come prepare dynamic crosslinking polymer and select retained when, available oligomer swell gel；It is prepared using plasticizer Dynamic crosslinking polymer simultaneously selects when being retained, available plasticizer swell gel；Dynamic is prepared using ionic liquid Cross-linked polymer simultaneously selects when being retained, available ionic liquid swell gel.
In above-mentioned preparation method, prepared compound liquid concentration is according to the structure of selected reactant, molecular weight, dissolution It depending on degree and required dispersity, is not particularly limited, preferred compound liquid concentration is 0.1~10mol/L, more preferably For 0.1~1 mol/L.
The specific method of preparation hydridization dynamic crosslinking polymer material is stirred using melting, usually by raw material anti- Answer directly be stirred in device or heating melting after be stirred reaction, such mode is generally gas, liquid or molten in raw material It is used in the case where the lower solid of point.In general, hybrid reaction temperature is controlled at 0-200 DEG C, preferably 25-120 DEG C, more preferably 25-80 DEG C, mixing time is controlled in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into properly Mold in, at 0-150 DEG C, under the conditions of preferably 25-80 DEG C of temperature, place 0-48h, obtain polymer samples.
It is mixed with the specific method of hydridization dynamic crosslinking polymer material using melting extrusion, is usually to add raw materials into Extrusion blending reaction is carried out into extruder, extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be directly cast It is cut into suitable dimension after molding, perhaps carries out obtained extrusion sample to utilize injection molding machine or moulding press system after being crushed Sample.Injection temperature be 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature is 0-280 DEG C, excellent Select 25-150 DEG C, more preferable 25-80 DEG C, clamp time 0.5-60min, preferably 1-10min, the preferred 4-15MPa of molding pressure. Batten can be placed in suitable mold, at 0-150 DEG C, under the conditions of preferably 25-80 DEG C of temperature, place 0-48h, obtain final Polymer samples.
Dynamic crosslinking polymer in the present invention is due to having based at least two supermolecular mechanisms and wherein at least one Body-object effect, so that dynamic crosslinking polymer obtained has excellent dynamic reversibility and good toughness, dynamic is handed over Possessed otherness between supermolecular mechanism not of the same race in linked polymer, so that polymer reflects the dynamic with hierarchy Can reverse effect, designed by suitable component selection and formula, material can be applied to military aerospace equipment, functional coating, biology The fields such as medicine, bio-medical material, the energy, building, bionical, intellectual material, have broad application prospects.
For example, making full use of self-repairability possessed by dynamic crosslinking polymer, can prepare with self-repair function Binder also can be used as bulletproof glass squeegee applied to the gluing of various types of materials；Preparation be can also be used for good plastic Property and the polymer of reuse can be recycled block sealing elements such as glue and sealing-plug, sealing ring etc., or application prepare it is wear-resisting Tear-proof taper knob etc. again；Dynamic reversibility based on supermolecular mechanism can be designed and be prepared with the resistance to of self-repair function Scratch coating is realized and is protected to the long-effective corrosion of basis material to extend the service life of coating；By suitably organizing sorting Design is selected and be formulated, the polymer material with self-repair function can be prepared, so as to the healing of mimic biology bulk damage Principle allows the material to carry out self-healing to internal or outer damage, eliminates hidden danger, and extend material uses the longevity Life, shows huge application potential in the fields such as military project, space flight, electronics, bionical.
For another example dynamic crosslinking polymer contains simultaneously, there are many supermolecular mechanisms, so that it can be embodied under external force Excellent toughness out, it is hereby achieved that thin polymer film, fiber or plate that toughness is splendid, are widely used in military, boat It, movement, the energy, the fields such as building；It can also be carried out as shape-memory material using when the external force is removed, material exists The deformation generated in loading procedure can be restored；The dilatancy that may be based on dynamic crosslinking polymer, by polymer application It is explosion-proof with fuel oil in recovering the oil, polymer material can also be applied to the magic effect that there is viscosity flow and high resiliency to convert for production Toy and body-building material；Based on the dynamic of dynamic crosslinking polymer, in the case where filling conductive filler, polymer composition Electric conductivity be easy to generate external force sensitive response, and then can be used for preparing force snesor.
Hydridization dynamic crosslinking polymer of the present invention is described further below with reference to some specific embodiments. Specific embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
The 4-vinylpridine of 1 molar equivalent, the alkene list of 1 molar equivalent hydrogen bonds group are added in No. 1 reactor (cyanuric acid and the chloro- 1- hexene of 6- keep molar ratio 4:1 to body, are dissolved in anhydrous dimethyl sulphoxide, at 80 DEG C under potassium carbonate catalysis Under be stirred to react 15 hours, the olefinic monomer of hydrogen bonds group is made), -5- glass of acrylamide [5] aromatic hydrocarbons of 1 molar equivalent it is (sharp Reacted with 5- amino-cup [5] aromatic hydrocarbons with acryloyl chloride and be made), the acrylamide -1- adamantane of 1 molar equivalent (utilize 1- amino Adamantane reacted with acryloyl chloride be made), the styrene of 10 molar equivalents, 0.1 molar equivalent potassium peroxydisulfate (KPS), stirring Uniformly, 80 DEG C are warming up to, after reacting 2h, suitable dimethyl sulfoxide (DMSO) is added, product is adjusted to certain density molten Then [2,3,5,6- tetra- bis- (the trifluoro methylsulphurs of { (diethylamino) methyl } phenylene-Isosorbide-5-Nitrae-of 0.01 molar equivalent are added in liquid Sour palladium)], 0.1 molar equivalent fumed silica, ultrasonic wave disperses 30min, after being uniformly mixed, a kind of dynamic is made and hands over Linked polymer solution.Increased with the viscosity that rotary viscometer measures the solution with the raising of mixing speed, can be used for Be prepared into liquid thickener carry out using.
Embodiment 2
100 mass parts deionized waters, 22 mass parts methyl acrylates, 10.5 mass parts propylene are added in No. 1 reactor - 4- glasss of amide [4] aromatic hydrocarbons (reacted and be made with acryloyl chloride using 4- amino-cup [4] aromatic hydrocarbons), 3 mass parts acrylamide -1- Adamantane (reacted and be made with acryloyl chloride using 1- aminoadamantan), 2 mass parts polyoxyethylene alkyl ether sulfate salt (AES), 10 mass parts 1- allyl pyridines, 1 mass parts azodiisobutyronitrile, are uniformly mixed, will be former in emulsifier Material carries out pre-emulsification, and then pre-emulsion is transferred in No. 2 reactors, 30mL deionized water is added, stirs evenly, and heats up To 80 DEG C, after reacting 4h, product is cooled to 40 DEG C hereinafter, adjusting product pH to 8~9, obtained modified propylene with sodium bicarbonate Sour methyl ester emulsions；31.5 mass parts water, 2 mass parts coconut oil diethanol amides, 1 mass parts 12 are added in No. 3 reactors Sodium alkyl benzene sulfonate, 0.3 mass parts mould inhibitor Z, 1 mass parts polyacrylate, 1 mass parts defoaming agent add after stirring 10min Enter 5 mass parts titanium dioxides, 3 mass parts lithopone, 1 mass parts propylene glycol, 11 mass parts precipitated calcium carbonates, 1 mass parts light to stablize Agent 770,2 mass parts pearl powders, 4 mass parts talcum powder, 0.2 mass parts calgon, 1.5 mass parts methylcellulose, 1 Mass parts silver trifluoromethanesulfonate after high speed dispersion 30min, is added 50mL modified acroleic acid methyl ester emulsions, stirs evenly and use water Viscosity is adjusted, a kind of dynamic crosslinking polymer emulsion is obtained.The lotion can be used as coating use, is coated in protective fence table Face has apparent strong reflecting effect at night, can heal automatically in coating damage cracking, extend making for outdoor coatings Use the service life.
Embodiment 3
By acrylamide -3-2 methoxyl group -5a, 9a- dihydro-dibenzo [b, d] pyrrole of 1 molar equivalent in No. 1 reactor It mutters and (is reacted and be made using 2- methoxyl group -5a, 9a- dihydro-dibenzo [b, d] pyrans -3- amine and acryloyl chloride), 1 molar equivalent 3- butene nitrile and 5 molar equivalents methyl acrylate mixing be dissolved in toluene, and be added 0.05 molar equivalent persulfuric acid Ammonium, cucurbit [8] urea of 0.5 molar equivalent, 0.02 molar equivalent nano ferriferrous oxide granule, ultrasonic wave dispersion after, heating Solvent is removed, by 1 mass parts product and 8 mass parts dimethicones, 0.15 after reaction to 80 DEG C of beginning polymerization reactions Mass parts graphene, 0.3 mass parts carbon fiber, the mixing of 0.02 mass parts gallium indium tin liquid metal, a small amount of deionized water, and stir Uniformly, it after ultrasonic wave dispersion, is placed in 80 DEG C of baking ovens and keeps the temperature 2h, obtain a kind of dynamic crosslinking polymer paste.The paste Object have very strong thermal conductivity, can be made into selfreparing thermal conductivity coating paste carry out using.
Embodiment 4
By the methyl acrylate of 10 molar equivalents, acrylamide-cup [4] aromatic hydrocarbons of 1 molar equivalent in No. 1 reactor The 5- ethylene of (reacted and be made using amino cup [4] aromatic hydrocarbons and acryloyl chloride), the 1- dodecylene of 1 molar equivalent, 1 molar equivalent Tetramethylethylenediamine (TEMED) mixing of base uracil, the potassium peroxydisulfate of 0.06 molar equivalent, 0.07 molar equivalent is dissolved in fourth Ketone after being stirred to react 1h at room temperature, adds a small amount of butanone, continues to stir 12h, then washes away butanone as far as possible with deionized water, Obtain a kind of dynamic crosslinking polymer jelly.The jelly has very strong bonding ability and good self-healing properties, Can be carried out as glazing compound using.
Embodiment 5
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 3.5 mass parts 2- amino pyrenes, 15 mass parts 6- amino are then added Cup [6] aromatic hydrocarbons continues after stirring 6h, 0.1 mass parts calcium chloride, 10 mass parts deionized waters is added, after being stirred, will mix It closes liquid to be put into 20 DEG C of insulating boxs after standing 12h, a kind of dynamic crosslinking polyalcohol hydrogel is made.The dynamic crosslinking polymer water Gel have good toughness, be made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, using cupping machine into Row extension test, rate of extension 50mm/min, measuring sample tensile strength is 0.95 ± 0.12MPa, and elongation at break is 472.42 ± 65.28, can be made into a kind of tack carry medicine stiff gel material carry out using.
Embodiment 6
The polyethylene glycol and 50mL pyridine that 9.5 mass parts end groups are NCO are added in No. 1 reactor, is stirred at room temperature It is completely dissolved to it, 1 mass parts [6- phenyl -2,2'- bipyridyl] -4- carboxylic acid and 0.1 mass parts ammonium chloride is added, continues to stir It is filtered after 4h, residual solvent is removed, with obtaining compound 1 after recrystallize with dichloromethane；By 5 mass part compounds 1,0.2 matter Amount part NaOH mixing is dissolved in 10 mass parts DMSO, and 5.7 mass parts 1- acrylamidos -2,4 are added, 6- trinitrobenzen (benefit With 2,4,6 trinitrobenzoic acid and propylene -1- amino reaction be made), 12 mass parts acrylamides-cup [5] aromatic hydrocarbons (utilize 4- Amino-cup [5] aromatic hydrocarbons and acryloyl chloride reaction are made), after leading to nitrogen deoxygenation, 0.02 mass parts potassium peroxydisulfate, 0.01 matter is added Part TEMED, 0.01 mass parts platinum chloride, 0.5 mass parts glass fibre are measured, after being quickly stirred, mixed liquor is put into 20 DEG C After standing 12h in insulating box, a kind of dynamic crosslinking polymer organic gel is made.The dynamic crosslinking polymer organic gel has Good toughness, 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 1.89 ± 0.23MPa, elongation at break be 512.21 ± 51.33, can be made into the gel toy with self-healing properties carry out using.
Embodiment 7
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, 10 molar equivalent of 4- azido -1,1'- biphenyl, zinc chloride 100 molar equivalents and a small amount of fumed silica and nanoscale ferroso-ferric oxide are dissolved in dimethylformamide, ultrasonic at room temperature 5min is warming up to 125 DEG C after being sufficiently mixed each component uniformly and is stirred to react, and obtains modified polypropene nitrile compound 1；It will be modified The ethyl isocyanate of the sum of polyacrylonitrile compound 1 and institute's hydroxyl equimolar equivalent reacts in dimethyl sulfoxide, obtains side The modified polyacrylonitrile product 1 of base amido-containing acid ester；Trifluoromethanesulfonic acid iron is added in suitable modified polyacrylonitrile product 1 Solution places it in after mixing evenly and is swollen 6h in dioctyl phthalate, and a kind of dynamic crosslinking polymeric plasticizer is made Swell gel.The plasticizer swell gel can also show certain shape memory characteristic under the action of an external magnetic field, can be with Be made a kind of shape-memory material carry out using.
Embodiment 8
3.8 mass parts anisaldehydes and 2.3 mass parts aniline are added in No. 1 reactor, are dissolved in 250 mass parts first together Alcohol is heated to reflux 12h in a nitrogen atmosphere.Then 1.5 mass parts NaBH are added4And continue at room temperature stir 12h, then plus Enter the hydrochloric acid solution of 10 mass parts 2mol/L, NH is added after stirring 10min4PF6Saturated aqueous solution, use deionized water after filtering Washing precipitating, obtains the object crosslinker compound 1 of white solid；10 mass parts acrylic acid first are added in No. 2 reactors Ester, 2.5 mass parts 4- acrylamide Benzo-18-crown-6s, 0.12 mass parts dibenzoyl peroxide (BPO), 0.12 mass Part N, N- dimethylaniline, 150 mass parts DMF, after being stirred to react 1h at room temperature, be added 50 mass parts dimethyl sulfoxides (DMSO) after Continuous stirring 72h, then washes away solvent with deionized water as far as possible, obtains compound 2.By 1 mass part compound 1,10 mass parts Compound 2,1 mass parts dicyclopentadienyl nickel mixed with polymers are dissolved in DMSO, and be added 0.5 mass parts pyridine, 1 mass parts graphene and The 1- ethyl-3-methylimidazole tetrafluoroborate ion liquid of 15 mass parts, ultrasonic wave dispersion are stood for 24 hours after mixing evenly, Then solvent is removed, a kind of dynamic crosslinking polymer ions liquid swell gel is obtained.The dynamic crosslinking polymer, which has, leads Electrically with pressure response, there is different conductivity under the action of different stress；A kind of strain gauge can be made into Carry out using.
Embodiment 9
10 mass parts methyl acrylates are added in No. 1 reactor, 5.1 mass parts acrylamides (utilize benzenephosphonic acid salt Phenylamino based phosphates and acryloyl chloride are reacted under the catalysis of triethyl group diamines and are made), the acrylamide -5- of 10.5 mass parts Acrylic acid -2- anthracene ester (the benefit of column [5] aromatic hydrocarbons (reacted and be made using 5- amino-column [5] aromatic hydrocarbons and acryloyl chloride), 3.5 mass parts Be made with 6- amino -2- hydroxyl anthracene and acryloyl chloride reaction), the 3- allyl -5- methyl-1 H- pyrrolo-es of 5.5 mass parts [2, 3-b] pyridine, 0.12 mass parts methyl ethyl ketone peroxide, the 4-dimethylaminopyridine of 0.12 mass parts, 180 mass parts chloroforms, room After being stirred to react 1h under temperature, 50 mass parts tetrahydrofurans (THF) are added and continue to stir 12h, are then washed away as far as possible with deionized water THF obtains product 1.The alkyl-blocked polyethylene glycol oligomer of 10 mass parts of mass parts product 1 and 20 is blended, mixing is equal After even, blend is placed in mold, 12 hours is kept the temperature at 80 DEG C, it is molten that a kind of dynamic crosslinking polymer oligomer is obtained after cooling Swollen gel.The tensile strength of the gel is 3.2MPa or so, and elongation at break can reach 863%, dynamic crosslinking polymer tool There are good toughness and self-reparing capability, the selfreparing sealing material with excellent sealing effect can be made into.
Embodiment 10
The methacryl trimethyl ammonium chloride of 1 molar equivalent, the acryloyl of 1 molar equivalent are added in No. 1 reactor 12 carbon of 1- of amine -5- column [5] aromatic hydrocarbons (reacted and be made using 5- amino-column [5] aromatic hydrocarbons and acryloyl chloride), 1 molar equivalent The 2 of alkene, 1 molar equivalent, 4,6- trimethyl styrenes, the methyl acrylate of 5 molar equivalents, 0.5 molar equivalent potassium peroxydisulfate, It is stirred and heated to 80 DEG C to be allowed to polymerize, product 1 is made；Take 100 mass parts products 1,5 mass parts AC foaming agents, 2 mass parts hard Resin acid barium, in mixing 30min on open mill, then blend glue stuff taking-up be put into suitable mold, using vulcanizing press into Row foaming, wherein molding temperature is 140-150 DEG C, clamp time 10-15min, pressure 10MPa, will bubble after molding Foam, which is placed in 60 DEG C of baking ovens, continues to cure 4h, obtains dynamic crosslinking polymer foams 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 2.34 ± 0.42MPa.Obtained polymer foams light specific gravity, soft, cracking Can be automatically repaired later, can be carried out as automotive interior material using.
Embodiment 11
The antioxidant of the 3- sulfydryl -1,2- propylene glycol and 0.01 molar equivalent of 1 molar equivalent is added in No. 1 reactor 168, the end-vinyl of 1 molar equivalent is added after mixing (uses vinyl chloride, 1,1 '-dioxane containing viologen compound Base -4,4'-Bipyridine salt compounded of iodine and 50mL dimethylformamide (DMF) react 4h at 50 DEG C, and with after recrystallize with dichloromethane It is made), it places it under 300W ultraviolet lamp and irradiates 30min, take out product 1 after cooling spare；By 10 mass parts products 1,0.5 The N-ethylmorpholine of mass parts, the TDI of 20 mass parts, 33 mass parts cucurbit [8] ureas, 3 mass parts water, 3 parts by mass Methylene chloride, It is uniformly mixed, is warming up to 80 DEG C, be quickly stirred to react with the blender of profession, by foam as in 60 DEG C of baking ovens after foaming Continue to cure 6h, obtains a kind of dynamic crosslinking polymer foams after cooling.It is made into 20.0 × 20.0 × 20.0mm The bulk sample of size carries out compression performance test using universal testing machine, and compression speed 2mm/min measures sample 50% Compressive strength is 1.46 ± 0.23MPa.Obtained polymer foams light specific gravity, resilience are good, can be made into stationery material Material carry out using.Under the action of pulling force, the synergistic action effect between Host-guest effect and hydrogen bond action keeps the dynamic poly- The tensile strength and elongation at break for closing object have obtained certain promotion；When the product is in polar solvent, hydrogen bond is made With decrease, the mechanical properties decrease of material, in polar solvent environment, Host-guest effect and hydrogen bond action show just The mechanics effect of friendship.
Embodiment 12
Phenanthroline -1,3 10 mass parts acrylic acid-(3- propyl diester) benzo [LMN] -3,8- are added in No. 1 reactor, 6,8- (2H, 7H)-tetrone (with 2- (3- hydroxypropyl) benzo [LMN] -3,8- phenanthroline -1,3,6,8- (2H, 7H)-tetrone and Acryloyl chloride reaction be made), 6 mass parts allyl cyclohexanes, 57 mass parts acrylamide -6- column [6] aromatic hydrocarbons (utilize 6- ammonia Base-column [6] aromatic hydrocarbons reacted with acryloyl chloride be made), 20 mass parts styrene after mixing, be added 1 mass parts benzoyl peroxide The formyl tert-butyl ester is warming up to 40 DEG C, after being stirred to react 2h, and product 1 is made；By 50 mass parts products 1,3 mass parts glass fibres, 3 mass parts nano talcs, 1 mass parts hollow glass microbead, 1.5 mass parts N, N '-dimethyl-N, N '-dinitroso pair Benzenedicarboxamide (foaming agent NTA) is added to progress mixing blending in small-sized internal mixer after mixing, will after mixing Sample takes out, and is put into twin-roll machine and suppresses flakiness, is cooled to is placed at room temperature for 30min later.It takes out and is kneaded print, place it in In suitable mold, foaming is carried out using vulcanizing press, wherein molding temperature is 90-105 DEG C, clamp time 10- 15min, pressure 10MPa finally obtain dynamic crosslinking polymer foams, with good rigidity and intensity.By its The bulk sample of 20.0 × 20.0 × 20.0mm size is made, carries out compression performance test, compression speed using universal testing machine For 2mm/min, measuring 10% compressive strength of sample is 7.73 ± 0.59MPa.Obtained polymer foams light specific gravity, intensity It is good, easily molded, can be carried out as the tool housing with self-healing properties using.
Embodiment 13
By 1 molar equivalent containing hydrogen silicone oil (average molecular weight about 20000, the weight of the repetitive unit of siliceous hydrogen and not siliceous hydrogen The molar ratio of multiple unit is about 1:2), 2 molar equivalents 4,4- dimethyl -1- amylene, 2 molar equivalent acrylamide -6- columns [6] virtue Hydrocarbon (is reacted with acryloyl chloride using 6- amino-column [6] aromatic hydrocarbons and is made), 1 molar equivalent allyl benzene, 1 molar equivalent 1- allyl Base 2,3,4,5,6- phenyl-pentafluoride and the quaternary ammonium base of silicone oil gross mass 7% are sufficiently mixed and are placed in mold.170 DEG C are warming up to, is protected Temperature 10 minutes obtains silicone elastomer after cooling demoulding.It is made into the dumbbell pattern of 80.0 × 10.0 × 2.0mm size Item, using cupping machine carry out extension test, rate of extension 50mm/min, measure sample tensile strength be 3.52 ± 0.38MPa, elongation at break are 679.32 ± 57.36.The product has good toughness, can be used for manufacturing a kind of selfreparing Coating or selfreparing elastomer, the sealing waterproof of the component applied to electronic product.
Embodiment 14
50 mass parts styrene, the bromo- 1- amylene of 10 mass parts 5-, 8 mass parts 2- allyls are added in No. 1 reactor Naphthalene, 57 mass parts acrylamide -7- column [7] aromatic hydrocarbons (reacted and be made with acryloyl chloride using 7- amino-column [7] aromatic hydrocarbons), 10 matter It measures bis- (1- tolimidazole -2- base) pyridines of part acrylate -2,6- and (uses bis- (the 1- tolimidazoles-of 4- hydroxyl -2,6- 2- yl) pyridine and acryloyl chloride reaction be made), 0.7 mass parts ammonium persulfate, the miscellaneous benzene of 0.1 mass parts ruthenium, 0.08 mass parts Zn4O (BTB)2(MOF-177), after being uniformly mixed, 80 DEG C are warming up to, product taking-up is dried after reacting 2h, obtains one kind Dynamic crosslinking polymer ordinary solid.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, utilizes tension test Machine carries out extension test, and rate of extension 10mm/min, measuring sample tensile strength is 17.35 ± 0.78MPa, elongation at break It is 88.24 ± 10.34.The product has good rigidity and intensity, and metal-organic presence makes it in ultraviolet light There is down fuel factor, can be used for manufacturing a kind of self-repairability plate carry out using.
Embodiment 15
The DL-1,4- dithiothreitol (DTT) of 2 molar equivalents, the 3- allyl-of 0.5 molar equivalent are added in No. 1 reactor 5- methyl-1 H- pyrrolo- [2,3-b] pyridine, 0.5 molar equivalent compound 1 (with the N- Butylurea of equimolar equivalent and different Cyanic acid allyl ester reacts under the catalysis of triethylamine), the change of the 4- vinyl biphenyl, 1.5 molar equivalents of 1.5 molar equivalents Close the antioxidant CA of object 2 (monohydroxy column [5] aromatic hydrocarbons and allyl iso cyanurate are reacted and be made) and 0.1 molar equivalent, mixing It after uniformly, places it under 300W ultraviolet lamp and irradiates 30min, after taking out cooling, it is spare that product 2 is made；By the product of 5 mass parts 2, the diethyl toluene diamine (DETDA), the dibutyl tin dilaurate (DY-12) of 0.5 mass parts, 5 mass parts of 1 mass parts Methylene chloride, the TDI of 15 mass parts, palladium (II) propionate of 0.2 mass parts, 8 mass parts water, 2 parts by mass Methylene chloride, 0.5 mass parts carbon nanotube, 0.5 mass parts graphene, are put into suitable mold after being dispersed with ultrasonic wave, are stirred with profession Machine after mixing, is warming up to 80 DEG C, it is made to react and foam, by foam as continuing to cure in 60 DEG C of baking ovens after the completion of foaming 6h obtains a kind of dynamic crosslinking polymer foams, is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, Using universal testing machine carry out compression performance test, compression speed 2mm/min, measure 70% compressive strength of sample be 0.95 ± 0.12 MPa.Obtained polymer foams light specific gravity and very soft, can be automatically repaired, in difference after breakage cracking Stress under have different resistivity, can be made into sensitive strain gauge carry out using.
Embodiment 16
Amino cup [4] aromatic hydrocarbons is added in No. 1 reactor and dimethyl acetamide is dissolved in methylene chloride in ice bath, adds Start to be stirred to react after entering acryloyl chloride, precipitating is filtered to remove after 4h, be concentrated under reduced pressure supernatant liquor and obtain crude product, with two Acrylamide-cup [4] aromatic hydrocarbons is made after recrystallizing to it in chloromethanes.The bromo- 6- hexane phenyl of 1- is added in No. 2 reactors With sodium azide in dry DMF solution, for 24 hours, 1- nitrine -6- hexane phenyl is made, by obtained 1- nitrine -6- in stirring Hexane phenyl, -5 alkynes of 1- hexene, stirring carry out the reaction of nitrine-alkynes click chemistry, compound 1 are made；Add in No. 3 reactors Enter 5 mass parts acrylamides-cup [4] aromatic hydrocarbons, 3 mass part compounds 1,1 mass parts N- [2- (2- oxo-pyrrolidine -1- base) second Base] acrylamide, bromo- 3, the 3- difluoropropenes of 5 mass parts 3-, 10 mass parts styrene and 0.1 mass parts AIBN, it is uniformly mixed Afterwards, 90 DEG C of beginning polymerization reactions are warming up to, after reacting 2h, compound 2 is made；Take 50 mass part compounds 2,3 mass parts nanometers Grade ferroso-ferric oxide, 7 mass parts expandable particles, after mixing, in mixing 30min on open mill, then blend glue stuff is taken It is put into suitable mold out, vulcanizing press is utilized to carry out foaming, wherein molding temperature is 110-120 DEG C, when molding Between be 10-15min, pressure 10MPa, foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h, dynamic is obtained after cooling Cross-linked polymer foamed material.Be made into the bulk sample of 20.0 × 20.0 × 20.0mm size, using universal testing machine into The test of row compression performance, compression speed 2mm/min, measuring 50% compressive strength of sample is 3.21 ± 0.63MPa.What is obtained is poly- Polymer foam light specific gravity, resilience are good, can be made into shape memory foam carry out using.
Embodiment 17
The dichloromethane of the polyethylene glycol that 10 mass parts molecular weight are 2000 and the drying of 50 mass parts is added in No. 1 reactor Alkane, is warming up to 50 DEG C, and 1.8 mass parts TDI are added after stirring and dissolving, continues to stir 2h, removes residual impurity, obtaining end group is The polyethylene glycol of NCO；The polyethylene glycol and 50 mass parts pyridines that 9.5 mass parts end groups are NCO are added in No. 2 reactors, It stirs to it and is completely dissolved at room temperature, 2 mass parts 2- aminophenanthrenes are added, continue to filter after stirring 4h, residual solvent is removed, with two It is luxuriant and rich with fragrance polyethylene glycol that end group is obtained after chloromethanes recrystallization；100 parts by mass Methylene chloride, 10 are added in No. 3 reactors Mass parts end group is luxuriant and rich with fragrance polyethylene glycol, 5 mass parts acrylamide perylenes (utilize 3- amino perylene and acryloyl chloride Under the catalysis of DMAP react be made), 0.1 mass parts sodium hydroxide, 30 mass parts methyl acrylates, add after mixing Then mixed liquor is put into after standing 12h in 20 DEG C of insulating boxs, removes molten by 0.2 mass parts potassium peroxydisulfate, 0.1 mass parts TEMED Agent, by product and 1 mass parts carbon fiber, 1 mass parts nano talc, 2 mass parts hollow glass microbeads, 0.5 mass parts chlorination Iron, the luxuriant ring of 15 mass parts duplex pyridine rings, 2 mass parts N, N '-dimethyl-N, N '-dinitrosoterephthalamine (hair Infusion NTA), after mixing, it is added to progress mixing blending in small-sized internal mixer, after mixing, sample is taken out, is put into Flakiness is suppressed in twin-roll machine, is cooled to is placed at room temperature for 30min later.It takes out and is kneaded print, place it in suitable mold, Foaming is carried out using vulcanizing press, wherein molding temperature is 90-105 DEG C, and clamp time is 10-15 min, and pressure is 10MPa finally obtains dynamic crosslinking polymer foams, with good rigidity and intensity.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 10% compressive strength of sample is 7.53 ± 0.58MPa.Obtained polymer foams light specific gravity, intensity are good, can be by it As automotive interior packing material carry out using.
Embodiment 18
The antioxidant of the 3- sulfydryl -1,2- propylene glycol and 0.01 molar equivalent of 1 molar equivalent is added in No. 1 reactor 168, be added after mixing the 1- octadecene of 0.4 molar equivalent, the styrene of 0.3 molar equivalent, 0.3 molar equivalent 2, 3,4,5,6- pentafluorostyrenes place it under 300W ultraviolet lamp and irradiate 30min, take out compound 1 after cooling spare；2 50 mass parts toluene, 6.4 1,1 '-diamino of mass parts-column [6] aromatic hydrocarbons, 3 mass part compounds 1,3.3 is added in number compound Mass parts HDI, 0.05 mass parts triethylamine, after being uniformly mixed, are warming up to 60 DEG C, the reaction was continued 2h, remove solvent, will produce Object moves on in Teflon mould, 20 mass parts dibutyl phthalates (DBP) is added, and mold is placed in 20 DEG C of constant temperature 12h is stood in case, and a kind of dynamic crosslinking polymeric plasticizer swell gel is made.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 50mm/min measures sample tensile strength For 2.23 ± 0.31MPa, elongation at break is 467.25 ± 45.32.The product has good toughness and self-repairability, can be with For manufacture a kind of toughness material carry out using.
Embodiment 19
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 N of 0.4 times of carboxyl molar equivalent, N- bis- is added in stirring to dissolution Picoline -2,6- diimine continues at room temperature after being stirred to react 12h, adds the 4- ammonia of 0.3 times of carboxyl molar equivalent The 4- aminoazabenzol of base-column [5] aromatic hydrocarbons and 0.3 times of carboxyl molar equivalent, the reaction was continued 12h remove solvent, and product 1 is made It is spare；The 30 mass parts polyether-ketones of mass parts product 1 and 50 are mixed, and 0.5 mass parts Metal Organic Molecular cage (MOC- is added 16) a kind of dynamic crosslinking polymer is made after extruding pelletization is molded in, 3 mass parts glass fibres, 3 mass parts carbon fibers Ordinary solid.The dumbbell shape batten for taking 80.0 × 10.0 × 2.0mm size carries out extension test using cupping machine, stretches Rate is 10 mm/min, and measuring sample tensile strength is 62.45 ± 4.35MPa, and elongation at break is 56.15 ± 6.48%, benefit With its surface hardness and high intensity, it can be made into the use of electric meter part, surface scratch can be automatically repaired more It closes.
Embodiment 20
Be added in No. 1 reactor the end-vinyl of 1 molar equivalent containing viologen compound (with vinyl benzyl chloro- 1, 1 '-dialkyl group -4,4'-Bipyridine salt compounded of iodine and 50mL dimethylformamide (DMF), react 4h, and use methylene chloride at 50 DEG C Be made after recrystallization), the vinyl cave ether of 1 molar equivalent is (by dimethyl -4- pyridone -2,6- dicarboxylic ester in DMF and carbon With propylene -1- bromine reaction in the mixed solution of sour potassium, compound 1, mixed solution of the compound 1 in ethyl alcohol and potassium hydroxide is made It is middle to restore carboxylate, compound 2 is made, under the action of thionyl chloride, by carboxyl chloride, compound 3 is made in compound 2, Compound 3 is made after reacting in pyridine solution with hexichol crown ether), the potassium peroxydisulfate of 0.01 molar equivalent and 0.01 molar equivalent TEMED, and enough toluene is added and is stirred for dissolving, then heat to 50 DEG C, after reacting 4h, remove solvent, be made and produce Object 1；10 mass parts acrylamides, 3 mass parts 1- allyl -3- methylimidazole chlorine, 2.8 mass parts are added in No. 2 reactors 2- methylpropene sodium sulfonate, 0.05 mass parts ammonium persulfate, 0.1 mass parts azo, two isobutyl imidazoline hydrochloride, 180mL bis- Chloromethanes is warming up to after being stirred to react 2h at 50 DEG C, and 50mL tetrahydrofuran (THF) is added and continues to stir 12h, then uses deionization Water washes away solvent as far as possible, obtains product 2；By product 1, the mass parts of product 2 and 1 carbon fiber, 1 mass parts nano talc, 50 Mass parts polypropylene, 10 mass parts polyacrylonitrile, 0.5 mass parts iron chloride, 5 mass parts pentanes are added to double after mixing It is squeezed out in screw extruder, finally obtains dynamic crosslinking polymer foams, with good intensity and toughness.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 1.87 ± 0.46MPa.It is obtained polymer foams light specific gravity, strong Spend, can be carried out as selfreparing elastic plate using.
Embodiment 21
1 molar equivalent polyacrylic acid (molecular weight 2000), 0.01 molar equivalent condensing agent 1- hydroxyl are added in No. 1 reactor Base benzotriazole (HOBT) and 0.012 molar equivalent activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), enough DMF are dissolved in, the 2- diazanyl anthracene that 0.5 times of carboxyl molar equivalent is added after mixing, 0.5 are extremely dissolved in stirring N- amino -3- piperidines the carboxylic acid amides of times carboxyl molar equivalent, the reaction was continued 12h remove solvent, it is spare that product 1 are made；At No. 3 35 mass parts products 1,1 mass parts dibutyl tin dilaurate, 10 mass parts cucurbit [7] ureas, 5 mass parts are added in reactor Conductive black, mixing are dissolved in DMSO, and the 1- ethyl-of 0.5 mass parts pyridine, 1 mass parts graphene and 15 mass parts is added 3- methyl imidazolium tetrafluoroborate ionic liquid, ultrasonic wave dispersion stand for 24 hours after mixing evenly, then remove solvent, that is, make Obtain a kind of dynamic crosslinking polymer ions liquid swell gel.The dynamic crosslinking polymer has good electric conductivity and selfreparing Ability, can be made into a kind of toughness supercapacitor carry out using.
Embodiment 22
A certain amount of 5- cyclo-octene -1,2- glycol, 2- (pyrimidine -2-base) pyrimidine -5- formic acid are mixed, three mole is controlled Several ratio is about 1:2, and using bicyclic ethyl carbodiimide and 4-dimethylaminopyridine as catalyst, methylene chloride is solvent, system Obtain the compound 1 of hydrogen bonds group；By the compound 1 of 10 mass parts, 20 mass parts cyclo-octene, 12 mass parts acrylamide- Acrylamide -1- the gold of 7- column [7] aromatic hydrocarbons (reacted and be made with acryloyl chloride using 7- amino-column [7] aromatic hydrocarbons), 2.6 mass parts Rigid alkane (react obtained uniformly mixed with acryloyl chloride using 1- aminoadamantan, using Grubbs bis- generations catalyst as catalyst, Using methylene chloride as solvent, and suitable platinum chloride is added, the polymer solution of fully reacting is poured into Teflon mould In, a kind of dynamic crosslinking polymer elastomer is obtained after solvent volatilization completely.It is cut into 80.0 × 10.0 × (0.08 ± 0.02) the dumbbell shape batten of mm size carries out extension test using cupping machine, and rate of extension 50mm/min measures sample Product tensile strength is 6.56 ± 0.52 MPa, and elongation at break is 469 ± 73%.Obtained polymer have stronger toughness and Good toughness, sample recycle after breaking, place it in mold and be bonded after 1-3h, can form again, carry out repeating to make With, can be made into a kind of good toughness material of intensity carry out using.
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, 6- amino-column [6] aromatic hydrocarbons of 1 molar equivalent is 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 The 1- aminoadamantan for entering 1 molar equivalent, is warming up to 80 DEG C, is stirred to react 2h, and compound 2 is made；It is added in No. 3 reactors The two of 1 molar equivalent are added after mixing in the 1 of 1 molar equivalent, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent Luxuriant armor alcohol, is warming up to 80 DEG C, is stirred to react 2h, and compound 3 is made；Be added in No. 4 reactors 1 molar equivalent 1,6- oneself 2,4,6- trimethyl benzylalcohols of 1 molar equivalent are added after mixing in the triethylamine of diisocyanate, 0.01 molar equivalent, rise Temperature is stirred to react 2h to 80 DEG C, and compound 4 is made；100 mass parts polyether polyol HPOP40 (hydroxyls are added in No. 5 reactors Value 20-23), 26 mass part compounds 1,3 mass part compounds 2,3.8 mass part compounds 3,3.2 mass part compounds 4, rise Temperature is to 80 DEG C, and after reacting 1h, 1.5 mass parts 2,3- epoxypropyltrimethylchloride chloride and 0.01 mass parts sodium hydroxide is added, 100 DEG C are warming up to, product 1 is made after reacting 2h；Obtained product 1,1 mass parts N, N- diformazan are added in No. 6 reactors Base benzylamine, 3 mass parts trimethylolpropanes, 0.5 mass parts dibutyl tin dilaurate (DY-12), 1 mass parts organic silicone oil, 5 mass parts water, 5 parts by mass Methylene chloride, 6 mass parts ethyl isocyanates are uniformly mixed, are warming up to 80 DEG C, with the stirring of profession Device is quickly stirred to react, and foam is obtained a kind of dynamic after cooling as curing 6h is continued in 60 DEG C of baking ovens after foaming Cross-linked polymer foamed material.Be made into the bulk sample of 20.0 × 20.0 × 20.0mm size, using universal testing machine into The test of row compression performance, compression speed 2mm/min, measuring 70% compressive strength of sample is 1.23 ± 0.13MPa.What is obtained is poly- Polymer foam light specific gravity, soft, resilience is good, and the inside packing material that can be made into cloth idol toy is made With.
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, nitrine One end of base equimolar equivalent is that the bipyridyl salt compounded of iodine of alkynyl is dissolved in tetrahydrofuran, under the catalysis of cuprous iodide and pyridine, Reaction obtains product 3 at 35 DEG C.100 mass parts products therefroms 3 are blended with a certain amount of cucurbit [8] urea, keep bipyridyl The molar ratio of base and cucurbit [8] urea is 4:1, and the antioxidant sodium dithionite of 2-5 mass parts is added, is sufficiently blended and is placed on In mold, compression molding obtains a kind of dynamic aggregation object elastomer.The elastomer has good toughness and temperature-responsive Property, it can be used as shape-memory material.
Embodiment 25
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, 4- amino-cup [4] aromatic hydrocarbons of 1 molar equivalent is 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 The dodecanol for entering 1 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 left-handed of 1 molar equivalent is added after mixing in the 1 of that equivalent, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent Carnitine is warming up to 80 DEG C, is stirred to react 2h, and compound 3 is made；100 mass parts polyether polyol are added in No. 4 reactors EP-8000 (hydroxyl value 22-26) and 0.5 mass parts triethylamine, are added 11.4 mass part compounds 1,3.6 mass after mixing Part compound 2,3.3 mass part compounds 3, are warming up to 80 DEG C, and after the reaction was continued 2h, product 1 is made；Product 1 is dissolved in chlorine In imitative, and 0.1 mass parts graphene is added, after ultrasonic wave is uniformly dispersed, solution is uniformly coated on to smooth polytetrafluoroethyl-ne Alkene plate surface obtains a kind of dynamic crosslinking polymer thin-film material after solvent volatilization is dry.It is cut into 80.0 × 10.0 The dumbbell shape batten of × (0.08 ± 0.02) mm size carries out extension test using cupping machine, and rate of extension is 50 mm/ Min, measuring sample tensile strength is 2.31 ± 0.38MPa, and elongation at break is 267 ± 35%.Sample recycles after breaking, will It is placed in mold and is bonded after 1-3h, can form a film, be reused again, can be returned as one kind using its property The antistatic isolation film of the property received uses.
Embodiment 26
Taking a certain amount of dendritic polyol compound, (using DMPA as photoinitiator, ultraviolet light is light source, by three allyls Base amine and 1,2- dithioglycol by the click addition reaction of mercaptan-alkene hydrocarbon be made level-one intermediate product after, then with triallylamine It continues through mercaptan-alkene hydrocarbon click addition reaction and second level intermediate product is made, pass through mercaptan-with 1,2- dithioglycol again later Three-level intermediate product is made in alkene click addition reaction, then reacts with triallylamine and level Four intermediate product is made, finally and calmly Final product is made by the click addition reaction of mercaptan-alkene hydrocarbon in the 3- sulfydryl -1,2- propylene glycol of amount) it is dissolved in toluene solvant It is configured to the solution of 0.1mol/L.Be added in No. 1 reactor the hexamethylene diisocyanate of 1 molar equivalent, 0.01 mole work as The triethylamine of amount is added 1- amino-column [6] aromatic hydrocarbons of 1 molar equivalent, is warming up to 80 DEG C, is stirred to react 2h after mixing, Compound 1 is made；The hexamethylene diisocyanate of 1 molar equivalent, three second of 0.01 molar equivalent are added in No. 2 reactors Amine is added 4- xenyl-methanol of 1 molar equivalent, is warming up to 80 DEG C, is stirred to react 2h after mixing, and compound 2 is made； It is added the 1 of 1 molar equivalent in No. 3 reactors, the triethylamine of hexamethylene-diisocyanate, 0.01 molar equivalent, after mixing, [6- phenyl -2,2'- bipyridyl] -4- carboxylic acid of 1 molar equivalent is added, is warming up to 80 DEG C, is stirred to react 2h, compound 3 is made； Take 20mL polyol compound solution to be added in the reaction flask of dried and clean, be added 13g compound 1,3.2g compound 2, 4.3g compound 1, the BHT antioxidant of 0.5mg, 0.2g triethylamine, 1.7g platinous chloride are protected in 80 DEG C of nitrogen after mixing evenly 2h is reacted under the conditions of shield.Polymer solution is poured into suitable mold later, is placed in 50 DEG C of baking ovens to place and be done for 24 hours Dry and further reaction, finally obtains membranaceous polymer samples.It is cut into 80.0 × 10.0 × (0.08 ± 0.02) The dumbbell shape batten of mm size carries out extension test using cupping machine, and rate of extension 50mm/min measures sample drawing Stretching intensity is 1.58 ± 0.24MPa, and elongation at break is 782 ± 121%.Obtained thin polymer film quality is softer, has one Fixed intensity and toughness, sample recycle after breaking, place it in mold and be bonded after 2-4h, can form a film again, carry out weight It is multiple to use, it can be used as a kind of recuperability cover film using its property.
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 (10)

1. a kind of dynamic crosslinking polymer containing combination supermolecular mechanism, which is characterized in that it contains at least two supermolecules The degree of cross linking of effect and at least one supermolecular mechanism is more than the gel point of its crosslinking, wherein the supermolecular mechanism is extremely Acted on less selected from Host-guest effect, ionization, close metal function, dipole-dipole effect, halogen bond effect, cation-π, Anion-π effect, benzene-fluorobenzene effect, the effect of π-π stacking, hydrogen bond action, metal-ligand effect, ion hydrogen bond action, freedom Base cation dimerization, based on wherein at least one-object effect, and at least one Host-guest acts on base In selected from ether, ring is luxuriant, combined main body of Cucurbituril, calixarenes, column aromatic hydrocarbons and inorganic organic ion skeleton.
2. the dynamic aggregation object according to claim 1 containing combination supermolecular mechanism, which is characterized in that the dynamic Contain at least two supermolecular mechanisms in polymer, is selected from following combination: Host-guest effect and hydrogen bond action, main body-visitor Body effect and metal-ligand effect, Host-guest effect and ionization, Host-guest effect and dipole-dipole effect, it is main Body-object effect and the effect of π-π stacking, Host-guest effect, metal-ligand effect and hydrogen bond action, Host-guest effect, Metal-ligand effect and the effect of π-π stacking.
3. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that described Dynamic crosslinking polymer has cross-linked structure, contains at least two supermolecular mechanisms and wherein at least one is the master Body-object effect, wherein the degree of cross linking of the supermolecular mechanism of all kinds is more than gel point.
4. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that described Dynamic crosslinking polymer has cross-linked structure, contains at least two supermolecular mechanisms and wherein at least one is the master The effect of body-object, wherein the degree of cross linking of at least one supermolecular mechanism more than gel point, at least one supermolecular mechanism The degree of cross linking is below gel point.
5. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that described Dynamic crosslinking polymer has cross-linked structure, contains at least two supermolecular mechanisms and wherein at least one is the master The effect of body-object, wherein the degree of cross linking of the supermolecule of all kinds in gel point hereinafter, but the sum of its degree of cross linking in gel Or more.
6. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that described Dynamic crosslinking polymer has cross-linked structure, contains at least two supermolecular mechanisms and wherein at least one is the master The effect of body-object, wherein the degree of cross linking of Host-guest effect more than gel point, the degree of cross linking of remaining supermolecular mechanism it With below gel point.
7. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that described Dynamic crosslinking polymer has cross-linked structure, contains at least two supermolecular mechanisms and wherein at least one is the master Body-object effect, wherein the sum of degree of cross linking of all Host-guest effects is in gel point hereinafter, the friendship of remaining supermolecular mechanism The sum of connection degree is more than gel point.
8. the dynamic crosslinking polymer according to claim 1 containing combination supermolecular mechanism, which is characterized in that constitute dynamic The recipe ingredient of state cross-linked polymer 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.
9. according to claim 1 to the dynamic crosslinking polymer containing combination supermolecular mechanism described in any one of 8, feature It is, form of the dynamic crosslinking polymer or its composition has following any: solution, lotion, cream, glue, gel, general Logical solid, elastomer, foamed material.
10. special according to claim 1 to the dynamic crosslinking polymer containing combination supermolecular mechanism described in any one of 8 Sign is, the dynamic crosslinking polymer or its composition are applied to following product: force snesor material, self-repairability coating, Self-repairability plate, self-repairability binder, adhesive, toughness material, shape-memory material, sealing material, energy storage device material Material, stationery material, toy material.
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CN114410284A (en) * 2022-03-29 2022-04-29 中国石油大学(华东) Micro-nano pore oil-water response membrane material, preparation method and application thereof
CN114410284B (en) * 2022-03-29 2022-06-17 中国石油大学(华东) Micro-nano pore oil-water response membrane material, preparation method and application thereof
CN117800620A (en) * 2024-02-27 2024-04-02 河北瑞昌玻璃纤维制品有限公司 Polymer coating high alkali-resistant glass fiber and preparation method thereof
CN117800620B (en) * 2024-02-27 2024-05-07 河北瑞昌玻璃纤维制品有限公司 Polymer coating high alkali-resistant glass fiber and preparation method thereof

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