CN108341943A - A kind of hydridization dynamic aggregation object and its application - Google Patents

A kind of hydridization dynamic aggregation object and its application Download PDF

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CN108341943A
CN108341943A CN201710055981.3A CN201710055981A CN108341943A CN 108341943 A CN108341943 A CN 108341943A CN 201710055981 A CN201710055981 A CN 201710055981A CN 108341943 A CN108341943 A CN 108341943A
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group
aggregation object
dynamic aggregation
hydrogen bond
compound
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不公告发明人
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Xiamen iron cloth Mstar Technology Ltd.
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Weng Qiumei
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers

Abstract

The invention discloses a kind of hydridization dynamic aggregation object, contain the cyclic annular organic boronic ester bond generated by organic boronic primitive and glycol elementary reaction and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, cyclic annular organic boronic ester bond and supermolecule hydrogen bond exist as polymerization linking point and/or the crosslinking linking point of dynamic aggregation object, are the necessary conditions to form or maintain dynamic aggregation object structure.Due to the dynamic reversibility of cyclic annular organic boronic ester bond and supermolecule hydrogen bond so that the dynamic aggregation object has self-repairability, reusability and recuperability；In addition, the dynamic aggregation object of special formulation, when by outer force effect, cyclic annular organic boronic ester bond and supermolecule hydrogen bond can be preferentially broken as that can sacrifice key so that material embodies good toughness.The dynamic aggregation object can be widely applied as self-repair material, toughness material, sealing material, squeegee, force snesor etc..

Description

A kind of hydridization dynamic aggregation object and its application
Technical field
The present invention relates to intelligent polymer fields, and in particular to one kind is made of dynamic reversible covalent bond and supermolecule hydrogen bond Hydridization dynamic aggregation object.
Background technology
Dynamic covalent chemical that dynamic chemical is combined in supramolecular chemistry and covalent chemical and the intersection to grow up Subject.Traditional molecular chemistry is concerned with stable covalent interaction, and dynamic chemical concern be then some relatively Weak noncovalent interaction and reversible covalent bonds.Among these, supramolecular chemistry be based on it is non-covalent it is intermolecular mutually Effect, for these noncovalent interactions compared with traditional covalent bond, bond energy is weaker, larger by thermodynamic effects, is formed by super Molecular structure to a certain extent for be not a dynamic stabilization system.And for dynamic covalent chemical, With some similar to the feature of supramolecular chemistry, reversible covalent bond " fracture " and " shape can just occur under appropriate conditions At "；And compared to supramolecular chemistry, the bond energy of the dynamic covalent bond in dynamic covalent chemical commonly greater than supermolecular mechanism power, It is even close with non-dynamic covalent bond, but due to dynamic covalent bond and the difference of supermolecular mechanism power substantially, dynamic is altogether The dynamic property of valence link then has very with supermolecular mechanism power in dynamic itself and its trigger condition (response condition) etc. Big difference.Dynamic covalent bond combines the invertibity of similar supermolecule noncovalent interaction and consolidating for covalent bond well Property, while other dynamics and trigger condition of feature are carried again so that it is widely used, and is constructing functional molecular Important work is shown with material, exploitation chemical sensor, regulation and control biomolecule, control smart molecule switch and machine etc. With.
Dynamic aggregation object is then that the novel polymeric system of one kind formed is linked by dynamic chemical key.According to link dynamic The difference of the dynamic chemical key of polymer, dynamic aggregation object can be divided into the physical dynamic aggregation object based on supermolecular mechanism power With the covalent type dynamic aggregation object based on dynamic covalent bond.By the covalent type dynamic aggregation object of dynamic reversible covalent bond formation, by The special nature possessed by dynamic reversible covalent bond, it may have outstanding feature.
But the fracture of covalent bond that is related to of the chemical balance process in conventional dynamic covalent polymer and being formed often is compared Relatively slowly, it and still usually needs to add catalyst or extraneous offer energy to accelerate equilibrium process.For example, being based on furans-horse Carry out acid imide Diels-Alder cycloaddition reaction products to generally require to carry out dissociation reaction under the high temperature conditions, and organic This reaction process carries out slow in solvent；The imine linkage that primary amine is generated with aldehyde reaction, is influenced strongly, to cause such by acid-base value Imine linkage must use within the scope of specific pH；The reversible exchange reaction of transamination then needs under the action of Special Proteins enzyme It could be formed；Based on the dynamic reversible key of alcoxyl nitrogen base, dissociation reaction temperature often will also reach 100-130 DEG C, meanwhile, alkane For the Ionization Potential of C-Centered Radicals that the dissociation of oxygen nitrogen base generates to oxygen and high temperature sensitive, the irreversible bonding thus brought can be to the performance of material It impacts；Dynamic aggregation object containing three thioester groups then needs to occur under ultraviolet light or heating condition dynamic State exchange reaction.The presence of such situation so that characteristic possessed by dynamic reversible covalent bond itself is at typical condition It is difficult to fully be embodied, needs to develop a kind of novel dynamic aggregation object, to solve existing in the prior art above-mentioned ask Topic.
Invention content
The present invention is directed to above-mentioned background, provides one kind containing cyclic annular organic boronic ester bond and is participated in by side hydrogen bond group The hydridization dynamic aggregation object of the supermolecule hydrogen bond of formation.The hydridization dynamic aggregation object stability is good, in general mild item There can be good dynamic reversibility under part, and reflect self-repairability, reusability, recuperability and bionical Mechanical property.
The present invention is achieved by following technical solution：
The present invention relates to a kind of hydridization dynamic aggregation objects, join containing cyclic annular organic boronic ester bond and by side hydrogen bond group With the supermolecule hydrogen bond of formation；Wherein, cyclic annular organic boronic ester bond and supermolecule hydrogen bond are linked as the polymerization of dynamic aggregation object It puts and/or is crosslinked linking point and exists, be the necessary condition to form or maintain dynamic aggregation object structure.
In embodiments of the present invention, the polymer in the hydridization dynamic aggregation object and its composition and material composition Chain topological structure is selected from line style, ring-type, branched, cluster, crosslinking and combinations thereof form.
A preferred embodiment according to the present invention, the hydridization dynamic aggregation object are non-crosslinking structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking in its gel point hereinafter, and the sum of degree of cross linking of the two be less than gel point.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking in its gel point hereinafter, and the sum of degree of cross linking of the two more than gel point.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking more than its gel point.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point, supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond The degree of cross linking below its gel point.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point, supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond The degree of cross linking more than its gel point.
In the present invention, the cyclic annular organic boronic ester bond and the side hydrogen bond group can be in same polymer On, it can also be on different polymer, wherein the side hydrogen bond group is located on polymeric chain independently of the ring-type In side group, side chain and the side group of organic boronic ester bond, the multilevel hierarchy of side chain at least one at.
The cyclic annular organic boronic ester bond in the present invention, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure need to be connected with a carbon atom by boron carbon key, and at least one is organic Group is keyed to by the boron carbon in boron atom；Indicate the aromatic ring of arbitrary first number, preferably hexatomic ring, and Contain two adjacent carbon atoms on aromatic ring, is located in the five-membered ring or hexatomic ring in cyclic annular organic boronic ester bond；Virtue Hydrogen atom on fragrant race's ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；Indicate with hydrogen atom, The connection of polymer chain, cross-linked network chain or any other suitable group/atom, boron atom and carbon atom are respectively by extremely A few connection access polymer chain forms the dynamic aggregation object；Difference on the same carbon atomIt can connect Ring is connected into, on different carbon atomsCyclization can also be connected, the ring includes but are not limited to aliphatic ring, aromatic series Ring, ether ring, condensed ring and combinations thereof.
The cyclic annular organic boronic ester bond in the present invention can be given birth to by organic boronic primitive and glycol elementary reaction At.
The organic boronic primitive in the present invention, preferably is selected from organic boron acidic group, organic boronic ester group, organic boronic Alkali, organic boron alkylhalide group.
The glycol primitive in the present invention preferably is selected from 1,2- glycol primitive, adjacent diphenol primitive, 1,3- glycol-baseds Member, 2- hydroxymethyl phenol primitives.
In embodiments of the present invention, the participation forms the side hydrogen bond group of supermolecule hydrogen bond comprising pendant hydrogen Key group and side chain skeleton hydrogen bond group.The side hydrogen bond group preferably comprises following any or several constituents：
Wherein, W is selected from oxygen atom, sulphur atom；X is selected from oxygen atom, sulphur atom, nitrogen-atoms；Wherein, a is to be connected with X atoms D number；When X is selected from oxygen atom or sulphur atom, a=0, D is not present；When X is selected from nitrogen-atoms, it is former that a=1, D are selected from hydrogen The small molecule alkyl of son, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da, Preferably hydrogen atom；I is divalent linking group, can be selected from singly-bound, hetero atom linker, molecular weight and is no more than the two of 1000Da Valence small molecule alkyl, molecular weight are more than the diatomic polymer chain residue of 1000Da；Q is end group, can be selected from hydrogen atom, hetero atom The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；Indicate with Main polymer chain skeleton, cross-linked network chain backbone, side chain (including its multilevel hierarchy) or any other suitable group/atom Connection；Wherein, I, D, Q any two or it is multiple between can connect cyclization, the ring includes but are not limited to aliphatic Ring, aromatic ring, ether ring, condensed ring and combinations thereof；3, the cyclic structure in 6 is the nonaro-maticity containing at least one N-H keys Or armaticity nitrogen heterocycle perssad, and be at least nitrogen-atoms there are two ring member nitrogen atoms, cyclic structure can be small molecule ring, can also It is macromolecular ring, is preferably 3~50 membered rings, more preferably 3~10 membered rings；The ring member nitrogen atoms of cyclic structure are each independently Carbon atom, nitrogen-atoms or other hetero atoms, the hydrogen atom on each ring member nitrogen atoms can be substituted, can not also be substituted.
In embodiments of the present invention, suitable main chain backbone hydrogen bond base is also optionally contained in hydridization dynamic aggregation object The supermolecule hydrogen bond action that group participates in.
In the present invention, the main chain backbone hydrogen bond group is referred to being located at non-cross-linked polymer main chain backbone and be moved Hydrogen bond group on state covalent cross-linking polymer network chain backbone, and wherein at least part of atoms is the composition portion of chain backbone Point, preferably comprise following constituent：
At least one of further preferably following constituent：
Wherein,Indicate the connection with main polymer chain skeleton, cross-linked network chain backbone.
In embodiments of the present invention, rational formula combination can be carried out at least with following several compounds and is used as raw material Reaction obtains the hydridization dynamic aggregation object containing cyclic annular organic boronic ester bond：
Organoboron compound (I) containing organic boronic primitive；Polyol compound (II) containing glycol primitive；Simultaneously Compound (III) containing organic boronic primitive and glycol primitive；Contain cyclic annular organic boronic ester bond and other reactive bases The compound (IV) of group；Without containing organic boronic primitive, glycol primitive and cyclic annular organic boronic ester bond but contain other reactions The compound (V) of property group；Wherein, organoboron compound (I), polyol compound (II) and compound (V) not separately as Raw material prepares dynamic aggregation object material.
The organoboron compound (I), polyol compound (II), compound (III), compound (IV), compound (V), it can be micromolecular compound of the molecular weight no more than 1000Da, can also be the macromolecular that molecular weight is more than 1000Da Compound；In organoboron compound (I), polyol compound (II), compound (III), it can contain or not contain it His reactive group.
In embodiments of the present invention, the form of the hydridization dynamic aggregation object and its composition can be solution, breast (including hydrogel, organogel, oligomer swell gel, plasticising solvent swell are solidifying for liquid, ordinary solid, cream, glue, elastomer, gel Glue, ionic liquid swell gel), foamed material etc..
In the preparation process of dynamic aggregation object, certain addible auxiliary agents can also be added, filler is blended to be total to With composition dynamic aggregation object, but these additives it is not necessary to.
In embodiments of the present invention, the hydridization dynamic aggregation object its can be applied to following material or product：From Prosthetic coating, self-repairability plank, self-repairability binder, sealing material, tough elastomer material, squeegee, toy, shape note Recall material.
Compared with prior art, the invention has the advantages that：
(1) dynamic aggregation is built as dynamic reversible key using cyclic annular organic boronic ester bond and side hydrogen bond group in the present invention Object takes full advantage of the dynamic of cyclic annular organic boronic ester bond and supermolecule hydrogen bond and the orthogonality and concertedness of the two, obtains With quick selfreparing, it is recyclable reuse characteristic dynamic aggregation object, room temperature or other can assign at use temperature Give the excellent self-repairability of material；Meanwhile material embodies good processing performance again, and be easily recycled and utilize again, This cannot achieve in existing polymeric system.In addition, (being helped as being added by optionally controlling other conditions Agent, adjustment reaction temperature etc.), it can accelerate or be quenched dynamic reversible balance under appropriate environment, dynamic aggregation object is made to be in Required state, this is more difficult inside existing supramolecular chemistry and dynamic covalent systems to accomplish.Simultaneously as not having Common covalent cross-linking more than gel point, polymer material can realize within largely selfreparing, moulding, recycling and again plus Work so that polymer material has broader application range and more permanent service life.
(2) the hydridization dynamic aggregation object in the present invention has good Modulatory character.It is used as the chemical combination of raw material by control The parameters such as the molecular structure structure of functional groups of organic boronic primitive and glycol primitive (especially) of object, functional group number, molecular weight, The dynamic aggregation object adjustable, widely used with different structure and appearance features, performance can be prepared.Simultaneously as side hydrogen bond Group has structure diversity, can be in a wider context to polymer by controlling the type and number of side hydrogen bond group Dynamic is combined collocation and regulation and control, based on the difference of itself and cyclic annular organic boronic ester bond dynamic, can obtain structure more Horn of plenty, performance are more various, dynamic reversible effect has more the polymer material of hierarchy.
(3) in the present invention, since side hydrogen bond group is in polymer pendant groups and/or side chain skeleton, group and chain Movement is more free, and dynamic is stronger, is particularly conducive to carry out selfreparing.Side hydrogen bond group in the present invention is preferably based on On the one hand the group of (thio) urethane/urea primitive is particularly suitable for forming the hydrogen bond with good dynamic, on the one hand again Compare hydrolytic resistance, it is upper more convenient preparing.This be other hydrogen bond systems it is incomparable.Further, since side hydrogen bond Group is located on polymeric chain independently of on side group, side chain and the side group of cyclic annular organic boronic ester bond, the multilevel hierarchy of side chain At at least one, cyclic annular organic boronic ester bond and the side hydrogen bond group in dynamic aggregation object can independently but also can not only cooperate with Ground plays a role, and is unlikely to cause another to act on because of the dissociation of one of them while fail.
(4) the cyclic annular organic boronic ester bond and supermolecule hydrogen bond contained in the dynamic aggregation object of special formulation is in outer force effect It can be broken in the form of " key can be sacrificed " down, to assign polymer material with excellent toughness.Due to supermolecule hydrogen Key is generally dissociated prior to cyclic annular organic boronic ester bond, so as to reach hierarchy toughening effect, and is answered in foreign impacts After power releases, cyclic annular organic boronic ester bond and supermolecule hydrogen bond can be bonded again again, selfreparing and recycling be carried out, with it His polymer material, which is compared, has embodied larger advantage.
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 implementation mode
The present invention relates to a kind of hydridization dynamic aggregation objects, join containing cyclic annular organic boronic ester bond and by side hydrogen bond group With the supermolecule hydrogen bond of formation；Wherein, the cyclic annular organic boronic ester bond and supermolecule hydrogen bond are as the poly- of dynamic aggregation object It closes linking point and/or crosslinking linking point and exists, be the necessary condition to form or maintain dynamic aggregation object structure, dynamic aggregation object In the cyclic annular organic boronic ester bond that contains and supermolecule hydrogen bond once dissociating, polymeric system is decomposed into following any Or appoint several units：Monomer, polymer chain segment, polymer cluster etc.；Meanwhile it can lead between dynamic aggregation object and said units It crosses the bonding of cyclic annular organic boronic ester bond and supermolecule hydrogen bond and dissociation realization mutually converts and dynamic reversible.
Term " polymerization " used is propagation process/effect of chain in the present invention, refers to that the reactant of lower molecular weight is logical Cross the process of product of the reaction formations such as polycondensation, addition polymerization, the ring-opening polymerisation synthesis with higher molecular weight.Among these, reactant Being typically polymerizing power (can spontaneously be polymerize, or can be gathered in initiator or outside plus under capable of acting on Close) the compounds such as monomer, oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two The product that kind or two or more reactants are polymerize is known as copolymer.It should be pointed out that described in the present invention " polymerization ", it includes the linear growth process of reactant molecule chain, include the branched process of reactant molecule chain, including reactant The annulation process of strand, but and the cross-linking process not comprising reactant molecule chain；That is " polymerization " is referred to except crosslinking Reactant molecule chain polymerization propagation process except reaction process.In embodiments of the present invention, " polymerization " also includes oversubscription Chain growth caused by sub- hydrogen bond action.
Term " crosslinking " used in the present invention, refer between reactant molecule and/or in reactant molecule by dynamic altogether The chemistry and/or supramolecular chemistry of valence link and/or supermolecule hydrogen bond connect to be formed with two dimension, three-dimensional cluster type and then form three Tie up the process of unlimited reticular pattern product.In cross-linking process, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, by Step forms cluster (can be two dimension or three-dimensional), and developing deeply is three-dimensional infinite network.For reactant in cross-linking process, viscosity is prominent Increase, start gel phenomenon occur, reaches reflecting point when a three-dimensional infinite network, referred to as gel point for the first time, also referred to as ooze Filter threshold value.The cross-linking reaction product (contained, similarly hereinafter) more than gel point has three-dimensional infinite network structure, cross-linked network It constitutes an entirety and across entire polymer architecture, cross-linked structure is relatively stable and secured；In gel point crosslinking below Reaction product does not form three-dimensional infinite network structure, is only locally lying in a small amount of two dimension or three-dimensional net structure, do not belonging to In the cross-linked network that can constitute an entirety across entire polymer architecture.It should be noted that the crosslinking in the present invention (structure) only includes the three-dimensional infinite network (structure) that gel point or more (contains, similarly hereinafter), and non-crosslinked (structure) then refers in particular to gel point The structures such as line style below, ring-type, branched and two dimension, three-dimensional cluster structure.
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key is formed by a kind of interaction between atom by share electron pair, and (100 DEG C are generally not more than) under typical temperature More difficult be broken with (be generally less than 1 day) in the usual time comprising but be not limited only to common carbon-carbon bond, carbon-oxygen bond, Carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen key, nitrogen-nitrogen key etc..Described in the present invention is " dynamic State covalent bond " refers to the special covalent bond of one kind that can carry out reversible fracture and formation under optimum conditions, in the present invention Refer in particular to the cyclic annular organic boronic ester bond generated by organic boronic primitive and glycol elementary reaction.
In embodiments of the present invention, the polymer in the hydridization dynamic aggregation object and its composition and material composition Chain topological structure is selected from line style, ring-type, branched, cluster, crosslinking and combinations thereof form.
Wherein, described " line style " structure, refer to polymer molecular chain presentation is rule or irregular long chain line Shape is generally formed by connecting by many repetitive units on a continuous length, 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 prepare.
Wherein, described " branched " structure refers on polymer molecular chain containing knots such as side chain, branch and bifurcated chains 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, cyclic structure are combined 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 hierarchy, such as It can continue to carry 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 formed, It is either formed by the chain transfer reaction of free radical in addition polymerization process or by radiating and chemically reacting in line style strand On extend branched structure and formed.Branched structure, which further carries out intramolecular and/or intermolecular reaction (crosslinking), to be generated 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.
In embodiments of the present invention, can only have one in the dynamic aggregation object and its composition and material composition The polymer of kind topographic morphologies can also be the mixture of the polymer there are many topographic morphologies.
The hydridization dynamic aggregation object can have on any appropriate position of polymer containing the ring-type Machine boric acid ester bond.For noncrosslinking dynamic aggregation object, cyclic annular organic boric acid ester can be both contained on main polymer chain skeleton Key can also contain cyclic annular organic boronic ester bond on polymer lateral chain/branch/bifurcated chain backbone；It is poly- for crosslinked dynamic Close object, dynamic covalent bond can be both contained on cross-linked network chain backbone, can also cross-linked network chain backbone side chain/ Contain cyclic annular organic boronic ester bond on chain/bifurcated chain backbone；The present invention is also not precluded in the side group and/or end group of polymer chain Contain cyclic annular organic boronic ester bond；Wherein, preferably on main polymer chain skeleton (for non-crosslinking structure) and crosslinked polymer Contain cyclic annular organic boronic ester bond on network chain backbone (for cross-linked structure).The cyclic annular organic boronic ester bond is in usual feelings Under condition, reversible fracture and regeneration can be carried out；Under suitable conditions, in dynamic aggregation object any position cyclic annular organic boron Acid esters key can participate in dynamic reversible exchange.
Wherein, for non-crosslinking structure, the polymer chain skeleton include main polymer chain skeleton and polymer lateral chain, The chain backbones such as branch, bifurcated chain.
Wherein, for cross-linked structure, the polymer chain skeleton includes the arbitrary segment being present in cross-linked network The chain backbones such as skeleton (i.e. cross-linked network chain backbone) and its side chain, branch, bifurcated chain.
Wherein, " main polymer chain " refers to thering is most chain links in polymer architecture if not otherwise indicated Several chains." side chain " refers to being connected with main polymer chain skeleton or cross-linked network chain backbone in polymer architecture The molecular weight for connecing and being distributed in chain backbone side is more than the chain structure of 1000Da；Wherein, the branch, bifurcated chain, refer to The molecular weight come out from main polymer chain skeleton or cross-linked network chain backbone or any other chain bifurcated is more than the link of 1000Da Structure；In the present invention, for the sake of simplicity, if not otherwise indicated, side chain, branch, bifurcated chain are collectively referred to as side chain.Wherein, institute " side group " stated refers to the molecular weight for being connected and being distributed in chain backbone side with polymer chain skeleton in polymer architecture Chemical group and molecular weight not higher than 1000Da are not higher than the short-side chain of 1000Da.For side chain and side group, can have more Level structure namely side chain can continue to carry side group and side chain, and the side chain of side chain can continue have side group and side chain, side therein Chain also includes branch and bifurcated chain isodesmic structure." end group " refers in polymer architecture with polymer chain skeleton It is connected and is located at the chemical group of chain backbone end；In the present invention, side group can also have end group under specific condition.
In embodiments of the present invention, the participation forms the side hydrogen bond group of supermolecule hydrogen bond comprising pendant hydrogen Key group and side chain skeleton hydrogen bond group.Wherein, side group hydrogen bond group refer to being present in polymer chain skeleton (including main chain and Side chain/branch/bifurcated chain backbone) side group on hydrogen bond group, and side group hydrogen bond group also is present in the multistage of side group In structure；Side chain skeleton hydrogen bond group refers to the hydrogen bond base being present on polymeric chain side chain (including branch and bifurcated chain) skeleton Group, and side chain skeleton hydrogen bond group also is present on the multilevel hierarchy of side chain.In the present invention, the cyclic annular organic boron Acid esters key and the side hydrogen bond group can be on same polymer, can also be on different polymer；When the ring When on same polymer, at least partly the side hydrogen bond group is only for shape organic boronic ester bond and the side hydrogen bond group Stand on the cricoid organic boronic ester bond, namely at least partly side hydrogen bond group and the cyclic annular organic boric acid ester Key is on different side group/side chains or its multilevel hierarchy, so as to the cyclic annular organic boronic ester bond and the side hydrogen bond base Group not only can independently again can synergistically play a role, be unlikely to because one of them dissociation and cause another act on simultaneously Failure；When on different polymer, the hydridization dynamic aggregation object forms for a kind of polymer, wherein comprising ring-type is contained The component of polymer of organic boronic ester bond and component of polymer containing side hydrogen bond group.In the present invention, it is preferred at least one Contain cyclic annular organic boronic ester bond and side hydrogen bond group on component of polymer simultaneously, preferably to play the association of Different Dynamic key Same effect.
In the present invention, when there are multiple component of polymer, each ingredient can be mutually perhaps incompatible；When in the presence of at least one It when the crosslinked ingredient of kind, can mutually disperse between heterogeneity, is mutually interspersed or partly interspersed, but the present invention is not limited only to This.
In embodiments of the present invention, at least partly it is to pass through polymer pendant groups in the supermolecule hydrogen bond action And/or the side hydrogen bond group on side chain (including branch and bifurcated chain) skeleton participates in being formed.Except with the side hydrogen bond base It is formed outside hydrogen bond action between group, it can also be with the hydrogen bond base that is present in any suitable position of other in dynamic aggregation object and its composition Group forms hydrogen bond, and including but not limited to (it includes that non-cross-linked polymer main chain backbone and dynamic are covalently handed over to main polymer chain skeleton Linked polymer network chain backbone), appoint in end group and to form hydrogen bond between the hydrogen bond group of one or more.Also, hydrogen bond group It can reside in small molecule, polymer and filler.
For the dynamic aggregation object with cross-linked structure, by cyclic annular organic boronic ester bond come constitute dynamic covalent cross-linking with And supermolecule hydrogen bond crosslinks are constituted by supermolecule hydrogen bond, wherein the degree of cross linking of dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks Can be more than respective gel point, it can also be in respective gel point hereinafter, but preferably dynamic covalent cross-linking and supermolecule hydrogen The sum of crosslinked degree of cross linking of key is more than the gel point of cross-linked polymer, and the degree of cross linking of preferred dynamic covalent cross-linking is in its gel Or more.When the crosslinking of cyclic annular organic boronic ester bond reaches gel point or more, as stress/strain response materials'use When, when being better able to embody the advantage of its dynamic, such as generating shear thickening behavior, viscous liquid and elasticity can be generated The transformation of solid is suitable as magic toy.
A preferred embodiment according to the present invention, the hydridization dynamic aggregation object are non-crosslinking structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking in its gel point hereinafter, and the sum of degree of cross linking of the two be less than gel point.In this embodiment, by cyclic annular organic Boric acid ester bond be formed by dynamic covalent cross-linking and by supermolecule hydrogen bond be formed by supermolecule hydrogen bond crosslinks may be at it is same In polymer chain, it can also be in different polymer chains independently of each other.In this embodiment, due to cyclic annular organic boron Acid esters key formed the degree of cross linking of dynamic covalent cross-linking and the degree of cross linking of supermolecule hydrogen bond crosslinks and its sum of gel point with Under, it can obtain with quick selfreparing, recyclable reuse characteristic and good processing performance, and be easily recycled simultaneously It utilizes again.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking in its gel point hereinafter, and the sum of degree of cross linking of the two more than gel point.In this embodiment, had by ring-type Machine boric acid ester bond, which is formed by dynamic covalent cross-linking and is formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond, is in same poly- In polymeric network structure.In this embodiment, the degree of cross linking of the dynamic covalent cross-linking formed due to cyclic annular organic boric acid ester key It, can be under stress/strain response with the degrees of cross linking of supermolecule hydrogen bond crosslinks in gel point hereinafter, the sum of its is more than gel point It realizes viscoelastic sex reversal, promotes the intensity of material.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, being formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond The degree of cross linking more than its gel point.In this embodiment, dynamic covalent cross-linking is formed by by cyclic annular organic boronic ester bond Same polymer chain or same polymer network structure are may be at supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond In, it can also be in different polymer chains or different polymer network structures independently of each other.In this embodiment, The degree of cross linking of the dynamic covalent cross-linking formed due to cyclic annular organic boric acid ester key is in its gel point hereinafter, can obtain with quick The characteristics such as selfreparing, recyclable reuse；And the degree of cross linking of supermolecule hydrogen bond crosslinks is then conducive to mend more than its gel point Fill the viscoplasticity or balanced structure of material matrix.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point, supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond The degree of cross linking below its gel point.In this embodiment, dynamic covalent cross-linking is formed by by cyclic annular organic boronic ester bond Same polymer chain or same polymer network structure are may be at supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond In, it can also be in different polymer chains or different polymer network structures independently of each other.In this embodiment, Due to cyclic annular organic boric acid ester key formed dynamic covalent cross-linking the degree of cross linking more than its gel point, can be in stress/strain Response is lower to realize viscoelastic sex reversal, promotes the intensity of material；And the degree of cross linking of supermolecule hydrogen bond crosslinks in its gel point hereinafter, then Be conducive to supplement the quick selfreparing of material, processing performance.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation object are cross-linked structure, are contained Cyclic annular organic boronic ester bond and the supermolecule hydrogen bond for participating in being formed by side hydrogen bond group；Wherein, by cyclic annular organic boronic ester bond The degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point, supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond The degree of cross linking more than its gel point.In this embodiment, dynamic covalent cross-linking is formed by by cyclic annular organic boronic ester bond It may be in same polymer network structure with supermolecule hydrogen bond crosslinks are formed by by supermolecule hydrogen bond, it can also mutually solely On the spot it is in different polymer network structures.In this embodiment, due to the dynamic of cyclic annular organic boric acid ester key formation The degree of cross linking of covalent cross-linking can realize viscoelastic sex reversal under stress/strain response, promote material more than its gel point Intensity；And the degree of cross linking of supermolecule hydrogen bond crosslinks is then conducive to the intensity and viscoplasticity to material matrix more than its gel point Further supplemented.
It is above-mentioned to be formed by dynamic covalent cross-linking by cyclic annular organic boronic ester bond and be formed by by supermolecule hydrogen bond super Molecule hydrogen bond cross-linked phase is mutually independent, refers to that the cyclic annular organic boronic ester bond and supermolecule hydrogen bond are in difference each independently Non-cross-linked polymer chain in or different crosslinking polymer networks in, it is mutually total between the crosslinking or non-cross-linked polymer of formation It is mixed or mutually interspersed.Constituted dynamic aggregation object, the dynamic between component are formed using mutually independent polymer It can be collocated with each other, independent effect, to embody preferably collaboration or orthogonal effect.
The cyclic annular organic boronic ester bond in the present invention, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure need to be connected with a carbon atom by boron carbon key, and at least one is organic Group is keyed to by the boron carbon in boron atom；Indicate the aromatic ring of arbitrary first number, preferably hexatomic ring, and Contain two adjacent carbon atoms on aromatic ring, is located in the five-membered ring or hexatomic ring in cyclic annular organic boronic ester bond；Virtue Hydrogen atom on fragrant race's ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；Indicate with hydrogen atom, The connection of polymer chain, cross-linked network chain or any other suitable group/atom, boron atom and carbon atom are respectively by extremely A few connection access polymer chain forms the dynamic aggregation object；Difference on the same carbon atomIt can connect Ring is connected into, on different carbon atomsCyclization can also be connected, the ring includes but are not limited to aliphatic ring, aromatic series Ring, ether ring, condensed ring and combinations thereof.
The cyclic annular organic boronic ester bond in the present invention can be given birth to by organic boronic primitive and glycol elementary reaction At.
The organic boronic primitive in the present invention, preferably is selected from organic boron acidic group, organic boronic ester group, organic boronic Alkali, organic boron alkylhalide group；
Wherein, the organic boron acidic group refers to two hydroxyl institute groups being connected by boron atom and with the boron atom At structural motifAnd boron atom therein need to be connected with a carbon atom by boron carbon key, and at least one Organic group is keyed to by the boron carbon in boron atom；
Wherein, the organic boronic ester group, refer to by boron atom, two oxygen atoms being connected with the boron atom and with Structural motif that the connected alkyl of this two oxygen atoms or silylation are formed (Wherein K1、K2、K3For Alkyl based on carbon, hydrogen atom or the silylation based on silicon, hydrogen atom pass through carbon atom or silicon atom and oxygen atom phase Even), and boron atom therein need to be connected with a carbon atom by boron carbon key, and at least one organic group passes through the boron Carbon is keyed in boron atom；
Wherein, the organic boronic alkali, refer to by boron atom, two negative oxygen ions being connected with the boron atom and Formed with the monovalence or bivalent cation of this two negative oxygen ion phase separations structural motif ( Wherein M1 +、M2 +For monovalent cation, preferably Na+、K+、NH4 +, M3 2+For bivalent cation, preferably Mg2+、Ca2+、Zn2+、Ba2 +), and boron atom therein need to be connected with a carbon atom by boron carbon key, and at least one organic group passes through the boron Carbon is keyed in boron atom；
Wherein, the organic boron alkylhalide group refers to two halogen originals being connected by boron atom and with the boron atom Son formed structural motif (Wherein, X1、X2For halogen atom, preferably chlorine atom and bromine atom), and it is therein Boron atom need to be connected with a carbon atom by boron carbon key, and at least one organic group is keyed to boron by the boron carbon On atom.
In addition, heretofore described organic boronic primitive, is further selected from lower structure：
Wherein D1、D2Difference, and it is each independently selected from hydroxyl (- OH), ester group (- OK1), alkali (- O-M1 +), halogen it is former Son (- x1), wherein K1、M1 +、X1Definition it is consistent with the foregoing description, which is not described herein again.
Particularly, when organic boronic primitive is connected with aminomethyl phenyl group, then aminomethyl phenyl boric acid primitive is formed, had Just like lower structure：
Wherein, A is organic boronic primitive, and three kinds of preferred structures are：
It indicates and hydrogen atom, small molecule hydrocarbyl chain, polymer chain, cross-linked network chain or any other suitable base The connection of group/atom.
Since aminomethyl phenyl boric acid primitive has higher reactivity, the ammonia of formation when being reacted with glycol primitive There is methylphenylboronic acid ester bond stronger dynamic reversibility, thus obtained dynamic aggregation object can show sensitive dynamic and imitate Fruit, therefore can be reacted as preferred organic boronic primitive.
The glycol primitive in the present invention preferably is selected from 1,2- glycol primitive, adjacent diphenol primitive, 1,3- glycol-baseds Member, 2- hydroxymethyl phenol primitives；
Wherein, 1, the 2- glycol primitives, are ethylene glycolAnd its substituted form lose it is at least one non- The residue formed after hydroxyl hydrogen atom；
Wherein, the adjacent diphenol primitive, for adjacent diphenolAnd its substituted form and its by hydridization shape Formula and combinations thereof loses the residue formed after at least one non-hydroxyl hydrogen atom；
Wherein, 1, the 3- glycol primitives, are 1,3-PDAnd its substituted form loses at least The residue formed after one non-hydroxyl hydrogen atom；
Wherein, the 2- hydroxymethyl phenol primitives are 2- hydroxymethyl phenolsAnd its substituted form and It is lost the residue formed after at least one non-hydroxyl hydrogen atom by hydridization form and combinations thereof.
The functional group in the present invention refers to above-described in the case where no other specialize Organic boron acidic group, organic boronic ester group, organic boronic alkali, organic boron alkylhalide group, 1,2- glycol primitive, adjacent diphenol primitive, 1, 3- glycol primitive, 2- hydroxymethyl phenols primitive or combination thereof etc..Wherein, the primitive (such as one of an organic boron atomic building A organic boron acidic group, an organic boronic ester group, an organic boronic alkali, an organic boron alkylhalide group), a 1,2- glycol Primitive, adjacent diphenol primitive, a 1,3- glycol primitive, a 2- hydroxymethyl phenol primitive are a functional group.
The supermolecule hydrogen bond action in the present invention is made by any appropriate supermolecule established by hydrogen bond With, the hydrogen atom being covalently attached to generally by the atom Z big with electronegativity and electronegativity is big, radius is small atom Y Z with Using hydrogen as medium between Y, generate the hydrogen bond link of Z-H ... Y shape formulas, wherein described Z, the Y for any appropriate electronegativity is big and It may be not same element that the small atom of radius, which can be same element, can be selected from the originals such as F, N, O, C, S, Cl, P, Br, I Son, more preferably F, N, O atom, more preferably O, N atom.Wherein, the supermolecule hydrogen bond action can be used as supermolecule Ring formation exists in polymerization and/or crosslinking and/or chain namely hydrogen bond can be played only and connect two or more segment lists Member, 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 two or more arbitrary combination, preferably at least part hydrogen bond group in ring formation or three of the above Supermolecule crosslinked action is played, the hydrogen bond that more preferably at least part side hydrogen bond group participates in being formed plays supermolecule crosslinked action.
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 are combined as a tooth.In following formula, the hydrogen of a schematically illustrate tooth, two teeth and three tooth hydrogen bond groups is distinguished Key bonding situation.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows：
The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is with regard to weak, Ke Yiqi To the effect for promoting dynamic aggregation object to keep balanced structure and raising mechanical property (modulus and intensity).If the number of teeth of hydrogen bond Few, then intensity is low, and the dynamic of hydrogen bond action can provide dynamic with regard to strong together with dynamic covalently cyclic annular organic boronic ester bond Energy.In embodiments of the present invention, the preferably more than hydrogen bond action of four teeth.
In embodiments of the present invention, the side hydrogen bond group preferably comprises following any or several knots is appointed to constitute Point：
Wherein, W is selected from oxygen atom, sulphur atom；X is selected from oxygen atom, sulphur atom, nitrogen-atoms；Wherein, a is to be connected with X atoms D number；When X is selected from oxygen atom or sulphur atom, a=0, D is not present；When X is selected from nitrogen-atoms, it is former that a=1, D are selected from hydrogen The small molecule alkyl of son, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da, Preferably hydrogen atom；I is divalent linking group, and the divalent of 1000Da is no more than selected from singly-bound, hetero atom linker, molecular weight Small molecule alkyl, molecular weight are more than the diatomic polymer chain residue of 1000Da；Q is end group, selected from hydrogen atom, heteroatom group The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；It indicates and poly- Close owner's chain backbone, cross-linked network chain backbone, side chain (including its multilevel hierarchy) or any other suitable group/atom Connection；Wherein, I, D, Q any two or it is multiple between can connect cyclization, the ring include but are not limited to aliphatic ring, Aromatic ring, ether ring, condensed ring and combinations thereof；3, the cyclic structure in 6 is nonaro-maticity or virtue containing at least one N-H keys Fragrance nitrogen heterocycle perssad, and be at least nitrogen-atoms there are two ring member nitrogen atoms, cyclic structure can be small molecule ring, can also be big Molecular Ring is preferably 3~50 membered rings, more preferably 3~10 membered rings；The ring member nitrogen atoms of cyclic structure are each independently carbon original Son, nitrogen-atoms or other hetero atoms, the hydrogen atom on each ring member nitrogen atoms can be substituted, can not also be substituted.In this hair In bright embodiment, side hydrogen bond group preferably is selected from carbamate groups, urea groups, thiocarbamate base and the above group Derivative.
Suitable side hydrogen bond group citing such as (but the present invention is not limited only to this)：
Wherein, m, n are the quantity of repetitive unit, can be fixed values, can also be average value, preferably smaller than 20, it is more excellent Choosing is less than 5.
Side hydrogen bond group has a structure diversity, including but not limited to hydrogen bond donor and receptor number, group size, with it is poly- Close the length and rigidity of the link between object chain；In addition, the quantity of the side hydrogen bond group connected on polymer chain also on a large scale may be used It adjusts.It participates in forming supermolecule hydrogen bond with side hydrogen bond group, intensity, dynamic, response, crosslink density can be obtained and on a large scale may be used The hydrogen bond action of tune, while by the regulation and control pair linked with polymer chain can control the dynamic of hydrogen bond, cross-linked polymer Glass transition temperature etc., and then effectively regulate and control every dynamic property of hydridization dynamic aggregation object, acquisition structure more horn of plenty, Performance is more various, dynamic reversible effect has more the polymer material of hierarchy.
In embodiments of the present invention, suitable main chain backbone hydrogen bond base is also optionally contained in hydridization dynamic aggregation object The supermolecule hydrogen bond that group's (including non-cross-linked polymer main chain backbone and dynamic covalent cross-linking polymer network chain backbone) participates in is made With, including intermolecular cross-linking, intramolecular cyclization and intermolecular polymerization etc., to enrich the performance and its adjustability of dynamic aggregation object.
In the present invention, the main chain backbone hydrogen bond group, wherein at least part of atoms are the component parts of chain backbone, It preferably comprises following constituent：
At least one of further preferably following constituent：
Wherein,Indicate the connection with main polymer chain skeleton, cross-linked network chain backbone.
In the present invention, one or more kinds of hydrogen bonds can be contained in same hydridization dynamic aggregation object or its composition Group.The hydrogen bond group can be formed by any appropriate chemical reaction, such as：Pass through carboxyl, acyl halide group, acid Covalent reaction between anhydride group, ester group, amide groups, isocyanate groups and amino is formed；Pass through isocyanate groups and hydroxyl Covalent reaction between base, sulfydryl, carboxyl is formed；By covalent between succinimide ester groups and amino, hydroxyl, sulfydryl Reaction is formed.
In the present invention, the supermolecule hydrogen bond action can be the process into Mobile state covalent cross-linking in dynamic aggregation object Middle generation；Can also be to be generated in advance after supermolecule hydrogen bond action again into Mobile state covalent cross-linking；It can also covalently be handed in dynamic After connection is formed, supermolecule hydrogen bond action is generated during dynamic aggregation object subsequent forming, but the present invention is not limited only to this.
The dynamic and the two of cyclic annular organic boronic ester bond and supermolecule hydrogen bond are taken full advantage of in the present invention just Hand over property and concertedness, obtain with quick selfreparing, it is recyclable reuse characteristic dynamic aggregation object, room temperature or other make It can assign material excellent self-repairability at a temperature of；Meanwhile material embodies good processing performance again, and be easy to back It receives and utilizes again, this cannot achieve in existing polymeric system.And it is used as the compound of raw material by regulation and control The parameters such as molecular structure, functional group number, molecular weight, the adjustable, purposes with different structure and appearance features, performance can be prepared Extensive dynamic aggregation object.
In embodiments of the present invention, rational formula combination can be carried out at least with following several compounds and is used as raw material Reaction obtains the hydridization dynamic aggregation object containing cyclic annular organic boronic ester bond：
Organoboron compound (I) containing organic boronic primitive；Polyol compound (II) containing glycol primitive；Simultaneously Compound (III) containing organic boronic primitive and glycol primitive；Contain cyclic annular organic boronic ester bond and other reactive bases The compound (IV) of group；Without containing organic boronic primitive, glycol primitive and cyclic annular organic boronic ester bond but contain other reactions The compound (V) of property group；Wherein, organoboron compound (I), polyol compound (II) and compound (V) not separately as Raw material prepares dynamic aggregation object material.
The organoboron compound (I), polyol compound (II), compound (III), compound (IV), compound (V), it can be micromolecular compound of the molecular weight no more than 1000Da, can also be the macromolecular that molecular weight is more than 1000Da Compound；In organoboron compound (I), polyol compound (II), compound (III), it can contain or not contain it His reactive group.
Other described reactive groups, refer to can spontaneously or can in initiator or light, heat, irradiate, urge Chemical reaction is carried out under the conditions of change etc. and/or physical action generates the group of common covalent bond and/or supermolecule hydrogen bond, suitably Group includes but are not limited to：Hydroxyl, carboxyl, carbonyl, acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, Sulfydryl, alkenyl, alkynyl, cyano, piperazine base, oximido, diazanyl, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxy group, Silicon hydrogen group, acrylate group, acrylamide group, maleimide base group, succinimide ester groups, norbornene Group, azo group, azido group, heterocyclic group, triazoline diketone, carbon radicals, oxygen radical, hydrogen bond group etc.；It is preferred that hydroxyl Base, amino, sulfydryl, alkenyl, isocyanate groups, epoxy group, acrylate group, acrylamide group, hydrogen bond group.
Other described reactive groups in the present invention, play the role of in system, first, performing the derivatization anti- Hydrogen bond group should be prepared, second is that described compound itself or its between other compounds or react with it straight between product The reaction for connecting other reactive groups forms common covalent bond and/or supermolecule hydrogen bond, so that describedization Molecular weight increase/the degree of functionality for closing object and/or its reaction product increases, and is formed between compound and/or its reaction product poly- It closes.
The organoboron compound (I) in the present invention, can following representation：
Wherein, A is organic boronic primitive；M is the number of A, m >=1；J is the substituent group on single A, or is two Or the linking group between multiple A；P is the number of group J, p >=1.
As m=1, p=1, J are the substituent group on single A；The J structures can be selected from following any：Molecular weight Small molecule alkyl, molecular weight no more than 1000Da are more than the polymer chain residue of 1000Da.
Work as m>When 1, A can be selected from same structure or a variety of different structures, at this time p >=1, and J is between two or more A Linking group；As p >=2, J can be selected from same structure or a variety of different structures；The J structures can be selected from following any Or appoint several：Singly-bound, hetero atom linker, molecular weight are big no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight In the divalent or multivalence polymer chain residue of 1000Da.
The polyol compound (II) in the present invention, can following representation：
Wherein, G is the module containing glycol primitive；N is the number of G, n >=1；L is the substituent group on single G, or For the linking group between two or more G；Q is the number of group L, q >=0.
The G can be single structure or various structures, i.e., the G contained in any polyol compound (II) can phase Together, it can also be different；It is selected from following any structure：Linear structure containing 1,2- glycol primitives contains 1,2- glycol-baseds Member or the cyclic structure of adjacent diphenol primitive, contain 1,3- glycol primitive or 2- hydroxyl first at the linear structure containing 1,3- glycol primitives The cyclic structure of base phenolic group member.
The linear structure for containing 1,2- glycol primitives can be selected from following any structure or its isomeric form：
Wherein, R1~R3For the univalent perssad being connected with 1,2- glycol primitives；Indicate that the position that G is connected with L (is tied in G Occur in structureThis meaning is represented, is no longer illustrated below)；Wherein, L and R1~R3It is connected to the two of 1,2- glycol primitives On a carbon atom.
Wherein, R1~R3It is each independently selected from following any structure：Hydrogen atom, heteroatom group, molecular weight are no more than Small molecule alkyl, the molecular weight of 1000Da are more than the polymer chain residue of 1000Da；
Wherein, the isomeric form of B1~B4 is each independently selected from any in position isomery, conformational isomerism, chiral photo-isomerisation Kind.
The cyclic structure for containing 1,2- glycol primitive or adjacent diphenol primitive, by two in glycol molecule residue Be connected by the same group between a carbon atom and formed, or by adjacent diphenol and its substituted form and its by hydridization form and its Combination is constituted；Wherein, cyclic structure is 3~200 membered rings, preferably 3~50 membered rings, more preferable 3~10 membered ring, the number of cyclic structure Amount is 1,2 or more, and the cyclic structure in G can be selected from following any：Aliphatic ring, aromatic ring, ether ring, condensation Ring and combinations thereof；
Wherein, in cyclic structure include 1,2- glycol primitive or adjacent diphenol primitive；
Wherein, L is connected on the ring member nitrogen atoms of cyclic structure；
Cyclic structure citing suitably containing 1,2- glycol primitive or adjacent diphenol primitive is such as：
The linear structure for containing 1,3- glycol primitives can be selected from following any structure or its isomeric form：
Wherein, R4~R8For the univalent perssad being connected with 1,3- glycol primitives；Indicate the position that G is connected with L；Wherein, L With R4~R8It is connected on three carbon atoms of 1,3- glycol primitives.
Wherein, R4~R8It is each independently selected from following any structure：Hydrogen atom, heteroatom group, molecular weight are no more than Small molecule alkyl, the molecular weight of 1000Da are more than the polymer chain residue of 1000Da；
Wherein, the isomeric form of C1~C6 is each independently selected from any in position isomery, conformational isomerism, chiral photo-isomerisation Kind.
The cyclic structure for containing 1,3- glycol primitive or 2- hydroxymethyl phenol primitives, it is residual by 1,3-PD molecule Between two carbon atoms in base by the same group be connected constitute, or by 2- hydroxymethyl phenols and its substituted form and its by Hydridization form and combinations thereof is constituted；Cyclic structure is 3~200 membered rings, preferably 3~10 membered rings, more preferable 3~6 membered ring, ring-type knot The quantity of structure is 1,2 or more, and the cyclic structure in G can be selected from following any：Aliphatic ring, aromatic ring, ether Ring, condensed ring and combinations thereof；
Wherein, in cyclic structure include 1,3- glycol primitive or 2- hydroxymethyl phenol primitives；
Wherein, L is connected on the ring member nitrogen atoms of cyclic structure and the carbon of 1,3- glycol primitive or 2- hydroxymethyl phenol primitives is former On son；
Suitably such as containing the citing of the cyclic structure of 1,3- glycol primitive or 2- hydroxymethyl phenol primitives：
As n=1, q >=1, L are the substituent group on single G；As q >=2, L can be selected from same structure or it is a variety of not Same structure；The L structures can be selected from following any or appoint several：Hydrogen atom, heteroatom group, molecular weight are no more than Small molecule alkyl, the molecular weight of 1000Da is inorganic small no more than 1000Da's more than the polymer chain residue of 1000Da, molecular weight Strand residue, molecular weight are more than the inorganic macromolecular chain residue of 1000Da.
Work as n>When 1, G can be selected from same structure or a variety of different structures, at this time q >=1, and L is between two or more G Linking group；As q >=2, L can be selected from same structure or a variety of different structures；The L structures can be selected from following any Or appoint several：Singly-bound, hetero atom linker, molecular weight are big no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight It is residual no more than the divalent of 1000Da or polyvalent mineral small molecule chain in the divalent or multivalence polymer chain residue of 1000Da, molecular weight Base, molecular weight are more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da.
Work as q>When 0, polyol compound (II) is connected and composed by above-mentioned L between two or more G.At this point, formed The typical structure of suitable polyol compound (II) can be exemplified below (but the present invention is not limited only to this)：
Wherein, g, j, x, y, z are each independently a fixed value or average value.
Particularly, as q=0, between two or more G by share a carbon atom, share a carbon-carbon single bond or The form for sharing a carbon-carbon double bond comes from different backgrounds and possess different abilities alcoholic compound (II), and suitable polyol compound (II) can be exemplified below (but the present invention is not limited only to this)：
The typical structure of above-mentioned polyol compound (II) is only that polyol compound (II) is better described in this condition Structure possessed by lower and propose, the typical structure of proposition only thus under the conditions of some most representative structures, rather than to this The restriction of invention protection domain.
Contain the compound (III) of organic boronic primitive and glycol primitive while described in the present invention, it can be with Following representation：
Wherein, A is organic boronic primitive, is specifically defined the definition that can refer to A in organoboron compound (I), here not It repeats again；X is the number of A, x >=1；As x >=2, A can be selected from same structure or a variety of different structures；G is to contain glycol-based The module of member, is specifically defined the definition that can refer to module G in polyol compound (II), which is not described herein again；That y is G Number, y >=1；As y >=2, module G can be selected from same structure or a variety of different structures；T between two or more A or Linking group between two or more G or between A and G, the T structures can be selected from following any or appoint several：It is single The divalent of key, hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the two of 1000Da Valence or multivalence polymer chain residue, are specifically defined the definition that can refer to group J in organoboron compound (I), no longer superfluous here It states；V is the number of group T, v >=1；As v >=2, T can be selected from same structure or a variety of different structures.
In organoboron compound (I), polyol compound (II), compound (III), in addition to containing organic boron acidic group Member, outside glycol primitive, it is also an option that property contain other reactive groups.
The compound (IV) containing cyclic annular organic boronic ester bond and other reactive groups described in the present invention, can With following representation：
Wherein, E is the module containing cyclic annular organic boronic ester bond；U is the number of module E, u >=1；Y is on individual module E Substituent group, or be the substituent group on individual module E and the linking group between two or more module E, and at least One group Y is connected with the boron atom of cyclic annular organic boronic ester bond, and the carbon of at least one group Y and cyclic annular organic boronic ester bond are former Son is connected；Wherein, at least one other reactive group is contained at least one group Y, and is contained in all group Y Other reactive group numbers be more than or equal to 2；R is the number of group Y, r >=2.
The module E containing cyclic annular organic boronic ester bond, can following representation：
Wherein,Indicate the small molecule hydrocarbon for being no more than 1000Da with group Y or hydrogen atom, heteroatom group, molecular weight The connection of the polymer chain residue of base, molecular weight more than 1000Da.
In the present invention, the described module E containing cyclic annular organic boronic ester bond, can through the invention in be previously mentioned It is any or appoint several organic boronic primitive A and it is any or appoint several module G containing glycol primitive by glycol primitive with Obtained by condensation reaction or ester exchange reaction between organic boronic primitive.
As u=1, Y is the substituent group on individual module E, and Y can be selected from same structure or a variety of different structures, and And the quantity of other reactive groups that contains of Y and structure must assure that can obtain the hydridization dynamic aggregation object；It is described Y structure can be selected from it is following any or appoint it is several：Small molecule alkyl, molecular weight of the molecular weight no more than 1000Da are more than The polymer chain residue of 1000Da.
Work as u>When 1, module E can be selected from same structure or a variety of different structures, and Y is the substituent group on individual module E Linking group between two or more module E, Y can be selected from same structure or a variety of different structures, and Y contain its The quantity and structure of his reactive group, which must assure that, can obtain the hydridization dynamic aggregation object；The Y structure is optional At least one of polymer chain residue from molecular weight no more than the small molecule alkyl of 1000Da, molecular weight more than 1000Da with And the divalent of singly-bound, hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than 1000Da Divalent or at least one of multivalence polymer chain residue.
For the compound (IV) containing cyclic annular organic boronic ester bond He other reactive groups, generally containing ring-type The monomer of organic boronic ester bond, the oligomer containing cyclic annular organic boronic ester bond, the prepolymer containing cyclic annular organic boronic ester bond. Compound (IV) can be prepared by any appropriate method, including pass through suitable organoboron compound (I) and polyol It is prepared by object (II).
Heretofore described compound (V), is not particularly limited its structure, and any appropriate does not contain organic boron Acidic group member, glycol primitive and cyclic annular organic boronic ester bond but compound containing other reactive groups is optional is used as this hair Compound (V) in bright.
A preferred embodiment according to the present invention, the hydridization dynamic aggregation object containing cyclic annular organic boronic key With line style or cyclic structure, preferably prepared by least one of following methods (but the present invention is not limited to This)：
The first, participates in reaction by least following components and generates cyclic annular organic boronic ester bond acquisition：It is at least one organic Boron compound (I), at least one polyol compound (II)；Wherein, organoboron compound (I) and polyol compound (II) are equal Contain at most Liang Ge functional groups；
Second, reaction is participated in by least following components and generates cyclic annular organic boronic ester bond and the acquisition of common covalent bond： At least one organoboron compound (I) and at least one polyol compound (II), or at least one organoboron compound (I), The combination of at least one polyol compound (II) and at least one compound (V)；Wherein, organoboron compound (I) and polynary Alcoholic compound (II) contains there are one functional group and other reactive groups, other are anti-containing at most two for compound (V) Answering property group；
The third, participates in reaction by least following components and generates cyclic annular organic boronic ester bond acquisition：At least one chemical combination Object (III) or it is at least one organoboron compound (I) or at least one polyol compound (II) or at least one have Machine boron compound (I) and at least one polyol compound (II)；Wherein, compound (III), organoboron compound (I), polynary Alcoholic compound (II) contains at most Liang Ge functional groups；
4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (IV), Or itself and at least one compound (V)；Wherein, compound (IV), compound (V) contain at most two other reactive bases Group.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation containing cyclic annular organic boronic key Object has branched structure, is preferably prepared (however, the present invention is not limited thereto) by least one of following methods：
The first, participates in reaction by least following components and generates cyclic annular organic boronic ester bond acquisition：It is at least one organic Boron compound (I), at least one polyol compound (II)；Wherein, in organoboron compound (I) and polyol compound (II) At least one compound contains at least three functional groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more；
Second, reaction is participated in by least following components and generates cyclic annular organic boronic ester bond and the acquisition of common covalent bond： At least one organoboron compound (I), at least one polyol compound (II)；Wherein, organoboron compound (I) and polyalcohol At least one compound contains at least one functional group and at least one other reactive group and functional group in compound (II) With the sum of other reactive group numbers no less than three, and a combination thereof does not generate the common covalent cross-linking of gel point or more；
The third, participates in reaction by least following components and generates cyclic annular organic boronic ester bond and the acquisition of common covalent bond： At least one compound (III), at least one compound (V) or this both, at least one organoboron compound (I) or At least one polyol compound (II) or at least one organoboron compound (I) and at least one polyol compound (II)； Wherein, compound (III), organoboron compound (I), polyol compound (II) contain at most Liang Ge functional groups and at least one Kind compound (III) or organoboron compound (I) or polyol compound (II) contain at least one other reactive group, and And a combination thereof does not generate the common covalent cross-linking of gel point or more；
4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (IV), Or itself and at least one compound (V)；Wherein, at least one compound (IV) or at least one compound (V) are containing at least Three other reactive groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more.
Another preferred embodiment according to the present invention, the hydridization dynamic aggregation containing cyclic annular organic boronic key Object has dynamic covalently cross-linked structure, preferably prepared by least one of following methods (but the present invention is not It is limited to this)：
The first, participates in reaction by least following components and generates cyclic annular organic boronic ester bond acquisition：It is at least one organic Boron compound (I), at least one polyol compound (II)；Wherein, organoboron compound (I) and polyol compound (II) contain There are at least two functional groups, and at least one organoboron compound (I) or at least one polyol compound (II) are containing at least Three functional groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more；
Second, reaction is participated in by least following components and generates cyclic annular organic boronic ester bond and the acquisition of common covalent bond： At least one organoboron compound (I), at least one polyol compound (II)；Wherein, organoboron compound (I) and polyalcohol The sum of functional group that compound (II) contains and other reactive group numbers no less than two, and at least one organoboron compound (I) or the sum of the functional group contained of at least one polyol compound (II) and other reactive group numbers are no less than three, and A combination thereof does not generate the common covalent cross-linking of gel point or more；
The third, participates in reaction by least following components and generates cyclic annular organic boronic ester bond and the acquisition of common covalent bond： At least one compound (III) or its at least one compound (V) or at least one organoboron compound (I) or at least A kind of polyol compound (II) or at least one organoboron compound (I) and at least one polyol compound (II)；Wherein, Compound (III), organoboron compound (I), polyol compound (II) contain at least two functional groups, and at least oneization It closes object (III) or organoboron compound (I) or polyol compound (II) contains at least three functional groups, or at least oneization It closes object (III) or organoboron compound (I) or polyol compound (II) contains at least one other reactive group, and its Combination does not generate the common covalent cross-linking of gel point or more；
4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (IV), Or itself and at least one compound (V)；Wherein, compound (IV), compound (V) contain at least two other reactive bases Group, and at least one compound (IV) or at least one compound (V) contain at least three other reactive groups, and its group Close the common covalent cross-linking for not generating gel point or more.
In the present invention, since the preparation process step for preparing dynamic aggregation object using above-mentioned several embodiments is simple, Operation is easy, and controllability is strong, therefore is the preferred embodiment of the present invention.
Dynamic aggregation object in the present invention is not limited only to prepare using above-described several embodiments, also may be used To be the combination of above-mentioned several embodiments or itself and other kind of embodiment.In every case organic boron chemical combination is utilized in embodiments Object (I), polyol compound (II), compound (III), compound (IV) carry out preparing dynamic aggregation object as raw material no matter It is in the form of raw material, also or is intermediate product with synthetic polymer or in the form of the compound of synthesis material Form, by its can guidance according to the present invention obtained, ought to be included in scope of patent protection of the invention.Equally Ground, those skilled in the art according to the present invention can also instruct, and reasonably implement to obtain institute using above-mentioned several compounds The dynamic aggregation object stated.
The heteroatom group being previously mentioned in the present invention can be any appropriate containing heteroatomic group, can Selected from following any group, but the present invention is not limited only to this：Halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine groups, silicon substrate, phosphorus Base, triazole, isoxazoles, amide groups, imide, thioamides base, enamine base, carbonate group, carbamate groups, thioesters Base, ortho acid ester group, phosphate-based, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, Carbamide, thioamides, phosphamide, phosphoramidite, pyrophosphoramide, cyclophosphamide, ifosfamide, thio-phosphamide, the rhizome of Chinese monkshood Acyl group, peptide bond, azo group, urea groups, isourea base, isothiourea group, allophanate group, thioallophanate base, guanidine radicals, amidino groups, Amino guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonate group, sub- sulphur Perester radical, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide, triazoline diketone.
The molecular weight being previously mentioned in the present invention is no more than the small molecule alkyl of 1000Da, typically contains 1 to 71 carbon Atom can contain heteroatom group, and can be free of has heteroatom group.Generally, the small molecule alkyl can be selected from By it is any in the following group, any it is unsaturated in the form of, it is any substituted form, any by hydridization form and its group It closes：C1-71Alkyl, ring C3-71Alkyl, phenyl, benzyl, aryl；Small molecule alkyl is preferably methyl, ethyl, propyl, propylene, fourth Base, butylene, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl；More preferably methyl, ethyl, propyl, benzene Base.
The molecular weight being previously mentioned in the present invention is more than the polymer chain residue of 1000Da, can be any appropriate polymerization Object chain residue includes but are not limited to carbochain polymer residue, heterochain polymer residue, elemento-organic polymer residue.Wherein, Polymer can be homopolymer, or appoint the copolymer of several monomers, oligomer or polymer composition；Polymer chain can be flexibility Chain or rigid chain.
Wherein, the carbochain polymer residue can be any appropriate macromolecular main chain mainly by carbon atom structure At polymer residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form, It is any by hydridization form and combinations thereof：Polyolefins chain residue, such as Polyethylene Chain residue, polypropylene chains residue, poly- isobutyl Alkene chain residue, polystyrene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain residue, polytetrafluoro Ethylene chain residue, polytrifluorochloroethylene chain residue, polyvinyl acetate chain residue, Polyvinylalkylethers chain residue, polybutadiene Alkene chain residue, polyisoprene chain residue, polychlorobutadiene chain residue, polynorbornene chain residue, polyvinyl alcohol residue etc.；It is poly- Acrylic compounds chain residue, such as polyacrylic acid chain residue, polyacrylamide chain residue, polymethyl acrylate chain residue, poly- methyl-prop E pioic acid methyl ester chain residue etc.；Polypropylene nitrile chain residue, such as polyacrylonitrile chain residue；It is preferred that Polyethylene Chain residue, polypropylene Chain residue, polystyrene chain residue, polyvinyl chloride chain residue, polybutadiene chain residue, polyisoprene chain residue, polyacrylic acid Chain residue, polyacrylamide chain residue, polyacrylonitrile chain residue.
The heterochain polymer residue, can be any appropriate macromolecular main chain mainly by carbon atom and nitrogen, oxygen, The polymer residue that the hetero atoms such as sulphur are constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, it is any It is substituted form, any by hydridization form and combinations thereof：Polyethers chain residue, such as polyethylene oxide chain residue, polycyclic oxygen Propane chain residue, PolyTHF chain residue, asphalt mixtures modified by epoxy resin fat chain residue, phenolic resin chain residue, polyphenylene oxide chain residue etc.；Polyester Class chain residue, such as polycaprolactone chain residue, poly- valerolactone chain residue, polylactide chain residue, polyethylene terephthalate Chain residue, unsaturated polyester (UP) chain residue, alkyd resin chain residue, polycarbonate chain residue, Biopolvester chain residue, liquid crystal polyester Chain residue etc.；Polyamine class chain residue, as polyamide chains residue, polyimides chain residue, polyurethane chain residue, polyureas chain residue, Polysulfide is for carbamic acid ester chain residue, Lauxite chain residue, melamine resin chain residue, liquid crystal polymer chain residue etc.；Polysulfide Class chain residue, such as polysulfones chain residue, polyphenylene sulfide chain residue；It is preferred that polyethylene oxide chain residue, PolyTHF chain residue, Asphalt mixtures modified by epoxy resin fat chain residue, polycaprolactone chain residue, polylactide chain residue, polyamide chains residue, polyurethane chain residue, polyureas chain Residue；The heterochain polymer residue can be reacted and be formed by click-reaction, such as CuAAC reactions, thiol-ene.
The elemento-organic polymer residue can be any appropriate macromolecular main chain mainly by silicon, boron, aluminium etc. The hetero atoms such as inorganic elements hetero atom and nitrogen, oxygen, sulphur, phosphorus constitute polymer residue, can be selected from it is any in the following group, appoint It is a kind of unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silicone-based polymers Chain residue, such as poly-organosilicon alkane chain residue, polysiloxane chain residue, poly-organosilicon borine chain residue, poly-organosilicon azane Chain residue, poly-organosilicon sulfane chain residue, poly- organophosphor siloxane chain residue, poly- organic metal siloxane chain residue；Organic boron Type of Collective object chain residue, such as poly- organo-borane chain residue, poly- organic boron sulfane chain residue, poly- have poly- organic boron azane chain residue Machine boron phosphine chain residue etc.；Organic phosphates polymer chain residue；Organic leadP Type of Collective object chain residue；Organic tin polymer chain is residual Base；Organo-arsenic Type of Collective object chain residue；Antimony organic Type of Collective object chain residue；It is preferred that poly-organosilicon alkane chain residue, poly organo Alkane chain residue, poly- organo-borane chain residue.
The molecular weight being previously mentioned in the present invention is no more than the small molecule silylation of 1000Da, can be any appropriate The small molecule silylation that molecular backbone is mainly made of the hetero atoms such as silicon atom and nitrogen, oxygen, sulphur, phosphorus, generally, described is small Molecule silylation can be selected from by it is any in the following group, any it is unsaturated in the form of, it is any substituted form, any By hydridization form：Silicon-carbon alkane chain residue, siloxane chain residue, silithiane chain residue, silazane chain residue；It is preferred that silicon-carbon alkane chain is residual Base, siloxane chain residue.
The molecular weight being previously mentioned in the present invention is no more than the inorganic molecules chain residue of 1000Da, can be arbitrary conjunction What suitable molecular backbone and side chain was mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic molecules chain residue, generally, the inorganic molecules chain residue can be selected from any in the following group, any It is unsaturated form, any substituted form, any by hydridization form：Silane chain residue, silicon oxide compound chain residue, Sulphur silicon compound chain residue, sulfur-nitrogen compound chain residue, phosphazene compound chain residue, phosphoric-oxygenic compound chain residue, borine chain are residual Base, boron-oxygen chain residue；It is preferred that silane chain residue, silicon oxide compound chain residue, phosphazene compound chain residue, borine chain are residual Base.
The molecular weight being previously mentioned in the present invention is more than the inorganic macromolecular chain residue of 1000Da, can be any appropriate Macromolecular main chain and side chain be mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic macromolecular chain residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted shape It is formula, any by hydridization form and combinations thereof：Polysilane chain residue, polysiloxane chain residue, polysulfide silicon chain residue, polysulfide nitrogen Chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene are for phosphonitrile chain residue, polyborane chain residue；Also selected from the following group In any inorganic macromolecular with residue, any inorganic macromolecular with residue being modified by surface：Zeolite type Molecular sieve, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecular sieve, diamond, graphite, graphene, graphite oxide Alkene, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, silica, silicon disulfide, silicon nitride, Silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, nitridation sulphur, silicon Change calcium, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, water aluminium Stone, gibbsite, corundum, titanium dioxide；It is preferred that polysilane chain residue, polysiloxane chain residue, polyphosphazene chain residue, polyborane chain Residue, by surface be modified graphene, by surface be modified carbon nanotube, by surface be modified carbon fiber, by table The silica of face modification, the silicon nitride being modified by surface, the silicon carbide being modified by surface, the silicic acid being modified by surface Salt, the glass fibre being modified by surface, the boron nitride being modified by surface.
The structure of small molecule alkyl, polymer chain residue, inorganic macromolecular chain residue is not particularly limited, it can To be straight chain type, branched chain type, multi-arm structural type, star-like, H-type, combed, dendritic, mononuclear type, polycyclic type, loop coil type, condensed ring Type, bridged ring type, the chain with cyclic structure, two and three dimensions cluster type and combinations thereof；It is residual in small molecule alkyl, polymer chain In base, inorganic macromolecular chain residue, soft segment can be contained, can also contain rigid chain segment, can also simultaneously contain it is flexible and Rigid chain segment.
Heretofore described " singly-bound ", refer in compound molecule between two atoms to share pair of electrons and The common covalent bond constituted, can be selected from carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond.
Heretofore described " hetero atom linker ", can be it is any appropriate contain heteroatomic linking group, It can be selected from following any or appoints several combinations：Ether, sulfenyl, carbonyl, sulfuryl, amide groups, carbonate group, carbamic acid Ester group, urea groups, divalent amido, trivalent amido, divalent silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalent phosphorus base, three valent phosphors base, divalent Boryl, trivalent boryl.
The relative molecular mass of term " molecular weight " used representative species in the present invention, for micromolecular compound, small For molecular radical and certain macromolecular compounds with fixed structure, macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And for oligomer, high polymer, oligomer residue, high polymer residue etc. have polydispersion The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the micromolecular 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 1000Da.
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, can also be the polymer chain that molecular weight is more than 1000Da Residue, suitable group citing is such as：Methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde radical, acetyl group, acetonyl etc..
Heretofore described " organosilicon radical " refers to mainly being constituted as skeleton using element silicon and protium Group can be the small molecule silylation that molecular weight is no more than 1000Da, can also be that molecular weight is organic more than 1000Da Silicon Type of Collective object chain residue, suitable group citing is such as：Silylation, siloxy group, silithiane base, silazane base etc..
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.
In the present invention, the carbon atom of any position is exchanged for heteroatoms the compound to be formed in hydrocarbon, is referred to as " miscellaneous hydrocarbon ".
Term " alkyl " used refers to the saturated hydrocarbyl for having 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 not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tertiary butyl, n-pentyl, 2- methyl butyls, 3- methyl butyls, 4- methyl butyls, n-hexyl, 2- methyl amyls, 3- methylpents Base, 4- methyl amyls, 5- methyl amyls, 2- ethyl-butyls, 3- ethyl-butyls, heptyl, octyl, nonyl, decyl.
Term " naphthenic base " used refers to the cyclic hydrocarbon of saturation in the present invention.Cycloalkyl ring may include specified carbon atom number. For example, 3 to 8 yuan of naphthenic base include 3,4,5,6,7 or 8 carbon atoms.The example of suitable naphthenic base includes but not limited to ring third Base, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl.
Term " aryl " used means the monocycle or more of any stabilization of at most 7 atoms in each ring in the present invention Ring carbon ring, wherein at least one ring are aromatic.The example of such aryl includes but not limited to phenyl, xenyl, naphthalene, connection Naphthalene, tetralyl, indanyl, anthryl, dianthranide base, phenanthryl, connection phenanthryl.
Term " heteroaryl alkyl " expression monocycle of the stabilization of at most 7 atoms or more in each ring used in the present invention Ring, wherein at least one ring is aromatic series and at least one ring contains selected from hetero atoms such as O, N, S, P, Si, B.In this definition model Heteroaryl alkyl in enclosing includes but not limited to acridinyl, carbazyl, cinnoline base, quinoxalinyl, quinazolyl, pyrazolyl, indoles Base, benzotriazole base, furyl, thienyl, thiophenyl, 3,4- propylidene dioxies thiophenyl, benzothienyl, benzofuran Base, benzodioxan, benzo dioxine, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, imidazole radicals, pyrazinyl, Pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, tetrahydroquinoline, thiazolyl, isothiazolyl, 1,2,4- triazolyls, 1,2,3- triazoles Base, 1,2,4- oxadiazolyls, 1,2,4- thiadiazolyl groups, cyanuro 1,3,5,1,2,4- triazine radicals, 1,2,4,5- tetrazines base and four Oxazolyl.
Aliphatic ring mentioned in the present invention can be any alicyclic ring or alicyclic heterocyclic, and ring member nitrogen atoms are respectively independent Ground is carbon atom or hetero atom；It is former that the hetero atom can be selected from nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron Son；Hydrogen atom on aliphatic ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；It can be monocycle Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure.Generally, the aliphatic ring packet It includes but is not limited to ring C3-200Alkane, azietine, side's acid, cyclobutanedinone, semi-square acid, cyclopentadienyl, pyrrolidines, thiazolidine, dihydro are different Oxazole, oxazolidines, cyclohexene, piperidines, norbornane, norbornene, norbornadiene, 1,4,7- 7-triazacyclononanes, torus Rattan is peaceful, thiophene, pyrroles, imidazoles, oxazole, isoxazoles, thiazole, isothiazole, pyrazoles etc.；The preferred cyclopropane of aliphatic ring, Cyclobutane, pentamethylene, hexamethylene, cycloheptane, cyclooctane, cyclononane, cyclodecane, thiophene, pyrroles；The aliphatic ring is more excellent Ring selection propane, cyclobutane, pentamethylene, hexamethylene.
Aromatic ring mentioned in the present invention can be any aromatic ring or heteroaromatic, and ring member nitrogen atoms are respectively independent Ground is carbon atom or hetero atom；It is former that the hetero atom can be selected from nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron Son；Hydrogen atom on aromatic ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；It can be monocycle Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure.Generally, the aromatic ring packet Include but be not limited to phenyl ring, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5- triazines, indenes, dihydroindene, indoles, iso-indoles, purine, Naphthalene, anthracene, dihydroanthracene, xanthene (xanthene), thio xanthene, phenanthrene, dihydro phenanthrene, 10,11- dihydro -5H- dibenzo [a, d] cycloheptane, Dibenzocycloheptene, 5- dibenzosuberenones, quinoline, isoquinolin, fluorenes, carbazole, iminodibenzyl, naphthalene second ring, dibenzo ring Octyne, azepine dibenzo cyclooctyne etc.；The preferred phenyl ring of the aromatic ring, pyridine.
The ether ring being previously mentioned in the present invention can be any ring containing ehter bond, and ring member nitrogen atoms are each independently For carbon atom, oxygen atom or hetero atom；The hetero atom can be selected from nitrogen-atoms, sulphur atom, phosphorus atoms, silicon atom, boron atom； Hydrogen atom on ether ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；It can be single ring architecture, more Ring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure.Generally, the ether ring includes but not limited to Ethylene oxide, tetrahydrofuran, oxinane, 1,4- dioxane, furans, crown ether etc.；The ether ring optimization ethylene oxide, four Hydrogen furans.
The condensed ring being previously mentioned in the present invention can contain the contractings such as amido bond, ester bond, acid imide, acid anhydrides to be any The ring of the chemical bond formed is closed, and ring member nitrogen atoms are each independently carbon atom or hetero atom；The hetero atom can be selected from nitrogen Atom, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom；Hydrogen atom on condensed ring ring member nitrogen atoms can be taken by any Replace for base, can not also be substituted；It can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, Nested ring structure.Generally, the condensed ring includes but are not limited to lactone, lactide, lactams, cyclic imides, naphthenic acid Acid anhydride, cyclic peptide etc.；The preferred caprolactone of the condensed ring, lactide, caprolactam.
The single ring architecture that is previously mentioned in the cyclic structure of the present invention refers in cyclic structure containing only there are one ring, Citing is such as：
The multiring structure being previously mentioned is referred to containing two or more independent rings in cyclic structure, be illustrated such as：
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, citing is 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 are to each other by sharing the cyclic structure of two adjacent atomic buildings, and citing is 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, citing is 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, citing is such as：
For simplicity, the carbon atom number range in group is also labeled in the lower mark of C in the present invention with the form of subscripts It sets, indicates the carbon atom number that the group has, such as C1-10Indicate " there is 1 to 10 carbon atom ", C3-20Indicate " there is 3 to 20 A carbon atom "." undersaturated C3-20Alkyl " refers to C3-20Compound containing unsaturated bond in alkyl." substituted C3-20Alkyl " Refer to C3-20The substituted obtained compound of the hydrogen atom of alkyl." the C of hydridization3-20Alkyl " refers to C3-20Carbon atom in alkyl is miscellaneous The compound that atom replaces.When a group can be selected from C1-10When alkyl, it can be selected from any in range shown in subscript The alkyl of carbon atom number, you can be selected from C1、C2、C3、C4、C5、C6、C7、C8、C9、C10Any alkyl in alkyl.In the present invention, In the case of being not particularly illustrated, indicate to can be selected from any integer within the scope of this with the subscript that range format marks, the range Including two endpoints.
For simplicity, also the symbology by one kind with continuous serial number with similar meaning uses "~" in the present invention It is attached, indicates that the mark content connected with "~" includes each symbology between serial number section, such as group R1~R3That indicate is group R1, group R1, group R3；For another example that B1~B4 expressions is B1, B2, B3, B4.In this hair The symbology "~" occurred elsewhere in bright, represents such meaning.
It, all can be in the case of not specifying when the structure arrived involved in the present invention has isomer Any of which isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..
Heretofore described position isomery includes since substituent group, functional group or linking group are in glycol primitive or organic The upper difference set of boric acid primitive and the position heterogeneous structure generated.
For example, working as R1~R2When selected from same substituent group, the position heterogeneous structure of B2 can be：
For another example working as R4~R8When selected from same substituent group, the position heterogeneous structure of C1 can be
The conformational isomerism includes various differences of the atom in space caused by intramolecular is rotated around key in the present invention The conformational isomerism structure of arrangement and generation.
For example, the conformational isomerism structure of B1 can be
The chiral photo-isomerisation includes the chiral photo-isomerisation structure for being mirror each other in the present invention.
For example, when two carbon atoms when 1,2- glycol primitives are asymmetric carbon atom, the alloisomerism structure of B1 can be：
For another example when three carbon atoms in 1,3- glycol primitives are asymmetric carbon atom, the alloisomerism structure of C1 Can be：
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 by any substituent group.In the case of being not particularly limited, substituent group therein It is not particularly limited.
For a compound, a group or an atom, can simultaneously be substituted 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 Can include to be selected from the option of 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".For example, " polymerizeing in specification Contain cyclic annular organic boronic ester bond in the side group and/or end group of object chain " in "and/or", meaning is only to polymerize Containing cyclic annular organic boronic ester bond in the side group of object chain, or contain cyclic annular organic boric acid ester only on the end group of polymer chain Key, or contain cyclic annular organic boronic ester bond in the side group of polymer chain and end group simultaneously；For another example " cyclic annular in specification Organic boronic ester bond as dynamic aggregation object polymerization linking point and/or crosslinking linking point and exist " in "and/or", contain Justice is that cyclic annular organic boronic ester bond exists as the polymerization linking point of dynamic aggregation object, or cyclic annular organic boronic ester bond is made Exist for the crosslinking linking point of dynamic aggregation object, or cyclic annular organic boronic ester bond while the polymeric chain as dynamic aggregation object Contact exists with linking point is crosslinked.The conjunction "and/or" occurred elsewhere in the description of the present invention, represents such Meaning.
During preparing hydridization dynamic aggregation object, as in the organoboron compound (I) of raw material, compound (III) Organic boronic primitive, can exist in the form of organic boronic, organic boric acid ester, organic borate, organic halogen borine.It is organic In the presence of organic boronic primitive in boron compound (I) is in the form of organic boric acid ester, organic borate, organic halogen borine, During being reacted with polyol compound (II), compound (III), it can first pass through and hydrolyze to form organic boronic, Again new cyclic annular organic boronic ester bond is formed with the glycol elementary reaction in polyol compound (II), compound (III)；It is organic In the presence of organic boronic primitive in boron compound (I) is in the form of organic boric acid ester, it can also directly pass through ester exchange reaction New cyclic annular organic boronic ester bond is formed with the glycol elementary reaction in polyol compound (II), compound (III).
For the compound (III) simultaneously containing organic boronic primitive and glycol primitive, generally requires and pass through control Reaction condition and the suitable reaction promoter of addition, enable glycol primitive in compound (III) with it is of the same race or not of the same race The organic boronic primitive contained in compound (III) carries out reaction and forms cyclic annular organic boronic ester bond, to obtain dynamic aggregation Object.In one polymerization system, in addition to it can contain one or more kinds of compounds (III), can also contain simultaneously it is a kind of or A variety of organoboron compounds (I) and/or one or more kinds of polyol compounds (II).When raw material is selected from compound (III), To ensure the stability of raw material, preferentially selection exists the organic boronic primitive in compound (III) in the form of organic boric acid ester. In view of compound (III) preparation and preservation process are comparatively complicated, it is accordingly used in preparing the raw material group of dynamic aggregation object Divide and preferentially carries out collocation selection in organoboron compound (I) and polyol compound (II).
In embodiments of the present invention, for organoboron compound (I), polyol compound (II), compound (III), during forming dynamic monomer and/or prepolymer and/or polymer, in addition to utilizing two contained in compound Outside alcohol primitive and/or organic boronic primitive are reacted, other reactive groups that can also be contained simultaneously using it optionally with Other compositions are commonly covalently attached such as compound (IV) and/or compound (V) by polymerisation, and common reaction is constituted Dynamic aggregation object.Organoboron compound (I), polyol compound (II), compound (III) can also be participated in the pre-polymerization formed Object and/or polymer are blended with other compositions such as compound (IV) and/or compound (V), then pass through the common of other compositions Covalent linkage forms dynamic aggregation object.It can also be initially formed common covalent linkage, re-form the cyclic annular organic boric acid ester key of dynamic.
For compound (IV), generally by the phase between other reactive groups contained in compound (IV) Mutual reactance, or by other reactive groups contained in compound (IV) with compound (V) and/or by organic boron chemical combination Other contained in the prepolymer and/or polymer that object (I), polyol compound (II), compound (III) participation are formed are anti- Reacting to each other between answering property group, to obtain the dynamic aggregation object containing cyclic annular organic boronic ester bond.Can also directly by Other reaction-ity group reactions that compound (IV) contains in itself form common covalent linkage.Certainly, the present invention not only limit and this, 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, other reactive groups can be common total by being obtained by the reaction for such as following form Valence link, to be formed together dynamic aggregation object with cyclic annular organic boronic ester bond：Pass through the amino and compound contained in compound In the carboxyl that contains carry out condensation reaction and form amido bond；Pass through what is contained in the epoxy group and compound that contain in compound Amino, sulfydryl carry out ring-opening reaction and form secondary amine key, thioether bond；Under the action of initiator or outer plus energy, by compound The alkylene contained carries out free radical polymerization；Under the action of initiator or outer plus energy, pass through the alkylene contained in compound Carry out anion/cation polymerization；Pass through amino, hydroxyl, the sulfydryl contained in the isocyanate group and compound that contain in compound It carries out reaction and forms urea bond, urethane bond and thiocarbamate key；By the epoxy group that contains in compound into Row ring-opening polymerisation forms ehter bond；Under monovalence copper catalysis, pass through what is contained in the azido group and compound that contain in compound Alkynyl carries out CuAAC reactions；Thiol-ene points are carried out by the alkylene contained in the sulfydryl and compound that contain in compound Hit reaction；Pass through the addition reaction etc. between the double bond that contains in compound；Wherein, it is preferably able at not higher than 100 DEG C fast The mode of speed reaction is more preferably capable of the mode of fast reaction at room temperature, including but not limited to isocyanate group and amino, hydroxyl Base, the reaction of sulfydryl, acrylate reactions, thiol-ene click-reactions.
The suitable polymerization being previously mentioned in embodiments of the present invention can appoint by the way that this field is general A kind of suitable polymerisation carries out, and it is anti-to include but are not limited to condensation polymerization reaction, polyaddition reaction, ring-opening polymerisation It answers；Wherein, it is anti-to include but are not limited to Raolical polymerizable, anionic polymerisation, cationic polymerization for polyaddition reaction It answers, coordination poly-merization.
In specific implementation process, raw materials of compound can utilize above-mentioned any polymerisation process, pass through this field General any suitable polymerization technique implement.For example, when raw materials of compound obtains dynamic in the form of condensation polymerization When polymer, it can be implemented by polymerization techniques such as melt polymerization, polymerisation in solution, interfacial polymerizations；In another example working as compound When raw material obtains dynamic aggregation object in the form of free radical polymerization, bulk polymerization, polymerisation in solution, suspension polymerisation, breast can be passed through The polymerization techniques such as liquid polymerization are implemented；For another example when raw materials of compound obtains dynamic aggregation object in the form of ionic polymerization, It can be implemented by polymerization techniques such as polymerisation in solution, slurry polymerization, gas-phase polymerizations.
In preparation process, it is preferred to use solution polymerization process, emulsion polymerization technique prepare hydridization dynamic aggregation object.Institute Solution polymerization process, the emulsion polymerization technique stated, system viscosity can be reduced by having, and be easy to mass-and heat-transfer, be convenient for temperature control System, the advantage that can avoid hot-spot, the solution obtained, lotion are conducive to be coated, mix convenient for concentration or dispersion Operation.
In the present invention, for constitute hydridization dynamic aggregation object ring-type organic boronic ester bond organic boronic primitive, due to Electron deficient possessed by boron atom so that it easily generates bonding by nucleopilic reagent institute's attack containing unshared electron pair； And for constituting the glycol primitive of cyclic annular organic boronic ester bond, due to containing unshared electron pair on oxygen atom, with it is organic During boric acid primitive is in contact, cyclic annular organic boronic ester bond can be formed by dehydration condensation, ester exchange reaction etc., To constitute hydridization dynamic aggregation object.The present invention, which is exactly utilized possessed by organic boronic primitive and glycol primitive, reacts work Property, the dynamic aggregation object with good dynamic reversible characteristic has been made in dynamic reversibility possessed by cyclic annular organic boronic ester bond. Meanwhile the introducing of side hydrogen bond group so that dynamic aggregation object is a wide range of adjustable in intensity, dynamic and response etc., leads to The quantity for the side hydrogen bond that regulation and control introduce and its link structure with polymer chain are crossed, hydrogen bond density and glass transition can be obtained The controllable hydridization dynamic aggregation object of temperature.
In embodiments of the present invention, the form of the hydridization dynamic aggregation object and its composition can be solution, breast (including hydrogel, organogel, oligomer swell gel, plasticising solvent swell are solidifying for liquid, cream, glue, ordinary solid, elastomer, gel Glue, ionic liquid swell gel), 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, Lotion, cream, glue, ordinary solid, elastomer, gel and foamed material have their own characteristics each and advantage.Solution and lotion have good Mobility can fully demonstrate shear thickening effect in a fluid, while the coating that it has can also be used and reviewed one's lessons by oneself to prepare Overcoating layer.Cream is typically concentrated emulsions, and glue is typically the polymer of concentrated solution or lower glass transition temperatures, can be embodied good Good plasticity and fillable.The shape and volume of ordinary solid are relatively fixed, have better mechanical strength, can not be by The constraint of organic sweller or water.Elastomer has the general properties of ordinary solid, but has preferable elasticity simultaneously, and compares It is relatively soft, be conducive to through deformation to applied external force into row buffering.Gel then have good flexibility, can embody compared with Good changeability and resilience.Foamed material then has the advantages that density is low, light, specific strength is high, and part can also be overcome general The brittleness of logical solid and the relatively low problem of the mechanical strength of organogel, soft foam material also have good elasticity and soft relax Suitable characteristic.The material of different shape can have suitable purposes in different fields.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.
In the preparation process of hydridization dynamic aggregation object, mainly using mechanical foaming method, physical blowing method, chemical blowing process Three kinds of methods foam to dynamic aggregation object.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be gelled, cures and become foamed material.For shorten molding cycle can be passed through air and be added emulsifier or Surfactant.
Wherein, the physical blowing method, be realized using physical principle in the preparation process of dynamic aggregation object it is poly- The foaming for closing object, generally comprises following four method：(1) inert gas blown method, i.e., inert gas under pressurized condition It is pressed into molten polymer or pasty material, then decompression heating, makes the gas expansion of dissolving and foam；(2) low boiling point is utilized Liquid evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, keep liquid molten Enter in polymer beads, then heat and soften polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching uses liquid Body medium, which immerses in polymer, dissolves the solid matter added in advance, makes to occur a large amount of holes in polymer and be in foaming Shape, such as by solable matter salt elder generation and mixed with polymers, after being shaped to product, then product is put and is located repeatedly in water Reason dissolves out solable matter to get to open-celled foam product；(4) hollow microsphere is added in hollow microsphere method in the plastic Become obturator-type foamed plastics by solidification；Wherein, preferably by dissolving in inert gas and low-boiling point liquid in the polymer Method foam.Using physical blowing method, have operation Poisoning smaller, foaming raw material cost is relatively low, and foaming agent is without residual The advantages that staying body.Further, it is also possible to be prepared using freeze-drying.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally comprise following two methods：(1) thermal decomposable foaming agent foaming utilizes chemical foaming agent The gas decomposed to give off after heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, that is, utilize hair The chemical reaction occurred between two or more components in foam system, generating inert gas (such as carbon dioxide or nitrogen) causes Polymer is expanded and is foamed.Polymerisation and foamable reaction balance carry out in order to control in foaming process, to ensure that product has preferably Quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by adding in the polymer The method of chemical foaming agent is added to foam.
In the preparation process of hydridization dynamic aggregation object, mainly it is molded using moulded from foam, is injection-expansion molded and crowded Go out three kinds of methods of foaming to be molded dynamic aggregation object foamed material.
Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material is direct plungeed into die cavity to carry out foaming；Two-step method 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 is molded ratio Two-step method is easy to operate and production efficiency is high, 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 In certain flow rate injecting material melt, then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent Under the action of form nuclei of bubbles.After expansion stage and solidifying and setting stage are all happened at 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, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.Since it can not only realize continuous production, and it is more more competitive than injection-expansion molded in cost, because This is current most widely used foaming technology.
In the preparation process of hydridization dynamic aggregation object, those skilled in the art can prepare situation and mesh according to practical Marking polymer performance selects suitable foaming method and foamed material forming method to dynamic aggregation object foamed material system It is standby.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is half open-celled structure that leading to again, which has mutual disconnected structure then,.It, also can be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes：(1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be more than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are more than 0.4g/cm3, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm3, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm3, expansion ratio is more than 9.
Certain addible auxiliary agents, filler can also be added to collectively constitute in preparation process in hydridization dynamic aggregation object Dynamic aggregation object material, but these additives it is not necessary to.
In the preparation process of hydridization dynamic aggregation object material, the certain addible auxiliary agents being added can improve Material preparation process improves product quality and yield, reduces product cost or assign product certain distinctive application performance.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, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change Become the auxiliary agent of surface property, including antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescence increase White agent, delustering agent；Fire retardantization and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, stream Flat 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 amines, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamines, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl- N-2- hydroxypropyls caproic acid, N, N- dimethyl benzylamines, N, N- dimethyl cetylamines etc.；Organometallic catalysts, as stannous octoate, Dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cycloalkanes Sour cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；2. gathering Catalysts for olefin synthesis：As Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, Aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, three second Amine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth Deng；3. CuAAC catalysts：Concerted catalysis is shared by monovalence copper compound and amine ligand；Monovalence copper compound can be selected 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-yls) methyl] amine (TBTA), three [(1- tertiary butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts：Photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetones etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethyl Aminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, 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 Bis- (4- tert-butylcyclohexyls) esters of sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, 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 Use initiator：Such as 2,2,6,6- tetramethyl -1- oxygroups piperidines, 1- chloro-1-phenyls ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator：Such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, butter of tin/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, ensure material It can be successfully processed and be extended 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 phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) butane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) 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-terts 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 diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, it is such as thio Dipropionic acid dilauryl, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, phosphorous acid Three nonyl phenyl esters, three [2.4- di-tert-butyl-phenyls] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butylhydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphorous Acid esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Institute Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls； Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids 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- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-t-butyls Benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, the positive fourth positive group dithiocarbamates first of N '-two Sour nickel etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, it is used Light stabilizer dosage be not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the addible auxiliary agent, enable to polymer material during processing or use not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers：Lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate Antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.
Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.
Lubricant in the addible auxiliary agent can improve 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 fat 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 stearamides；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%.
Releasing 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 releasing 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 releasing 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, and elongation, flexibility and flexibility improve comprising but be not limited only to Under it is any or appoint several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, adjacent benzene two Formic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, O-phthalic It is bis- (13) esters of sour butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, right Phthalic acid two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Aliphatic ester Class, such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, ring Oxygen fatty-acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy Soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate, Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat Acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, inclined benzene three Acid esters, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), Dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene Dioctyl phthalate diisodecyl ester (DIDP), tricresyl phosphate (TCP), plasticizer consumption used are not particularly limited, generally 5- 20wt%.
Foaming agent in the addible auxiliary agent, can so that polymer samples foam pore-forming, to obtain it is light, every Heat, sound insulation, noise elimination, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.
Dynamic regulation agent in the addible auxiliary agent, can promote the dynamic of dynamic aggregation object, be usually Either free carboxyl group or the compound of electronics pair can be provided or be received with free hydroxyl, include but are not limited to water, hydrogen Sodium oxide molybdena, alcohol, carboxylic acid, lewis base, lewis acid etc..The dynamic of polymer can be adjusted by adding this analog assistant, to obtain The expected performance that must be optimized.Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt%.
The deleterious charge assembled in polymer samples can be guided or disappeared by the antistatic agent in the addible auxiliary agent It removes, makes it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several antistatic Agent：Anionic antistatic agent, such 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 acids sodium of N- lauryls-N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, Alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, it is such as poly- Allyl amide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, antistatic The preferred lauryl trimethyl ammonium chloride of agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used do not have It is particularly limited to, generally 0.3-3wt%.
Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid comprising 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；Nonionic, 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%.
Dispersant 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 solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms and stabilizes suspension comprising but be not limited only to following any or appoint several dispersants：It is cloudy Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, 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, polyvinyl alcohol etc..Wherein, the preferred neopelex of dispersant, naphthalene system are sub- Metilsulfate (dispersant N), fatty alcohol polyoxyethylene ether, dispersant dosage used are not particularly limited, 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 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 need not be limited especially 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 agent CBS), bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-talan Base) dibenzoxazine (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.
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：Settle 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 combustion inhibitor, 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, tricresyl phosphate Phenyl ester, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, generally For 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 It is not limited only to following any or appoints 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 ensure that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, its redispersibility can be improved 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, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.
Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency, to meet various demands such as its stability and application performance during production, storage and use, packet 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, aliphatic acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the addible auxiliary agent can ensure that the flat smooth of polymer coating film is uniform, 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%.
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 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, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, molybdenum disulfide, 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 microballoon, foaming are micro- Ball, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon Silica fibre, ceramic fibre, whisker etc..
The addible metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, Powder, nano particle and the fiber of gold etc. and its alloy.
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, protein, enzyme, hormone, raw lacquer, wood powder, shell powder, xylose, silk, Artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
In the preparation process of hydridization dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, heat are steady Determine agent, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.The preferred calcium carbonate of addible filler, barium sulfate, cunning Mountain flour, carbon black, glass microballoon, graphene, glass fibre, carbon fiber.
In the preparation process of hydridization dynamic aggregation object, the additive amount of dynamic aggregation object each component raw material is not done especially Restriction, those skilled in the art can prepare situation and target polymerization physical performance be adjusted according to practical.
In the preparation process of hydridization dynamic aggregation object, any appropriate material hybrid mode known in the art can be passed through The raw material centainly matched is prepared into dynamic aggregation object by mixing, can be interval, semicontinuous or continuous processing form Mixing；Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic aggregation object.The mixing of use Mode include but are not limited to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., In preferably solution be stirred, melt and be stirred and melting extrusion.Energy in material mixed process provides form But it is not limited only to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, injection Molding, compression molding, tape casting, calendering formation, cast molding.
The specific method for preparing hydridization dynamic aggregation object is stirred using solution, typically by raw material to dissolve or disperse Form mixing is stirred in respective solvent or in common solvent in the reactor.In general, hybrid reaction temperature Control is at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, and time control is mixed in 0.5-12h, preferably 1-4h. The product obtained after mixing can be poured into suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, be put - 48h is set to 0, polymer samples are obtained.
When preparing hydridization dynamic aggregation object material using the method as raw material using compound (IV), compound (V), usually It also needs to initiator is optionally added in a solvent and obtains dynamic aggregation object, Huo Zhejia in a manner of polymerisation in solution to cause polymerization Enter dispersant and oil-soluble initiator is configured to suspension and is moved in a manner of suspension polymerisation or slurry polymerization to cause polymerization State polymer, or addition initiator and emulsifier are configured to emulsion and obtain dynamic in a manner of emulsion polymerization to cause polymerization Polymer.Used polymerisation in solution, suspension polymerisation, slurry polymerization and emulsion polymerization method, be the technology of this field Personnel are known and widely used polymerization, can be adjusted according to actual conditions, no longer be developed in details here.
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, dichloromethane, 1,2- dichloros The positive fourth of ethane, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, isopropyl acetate, acetic acid Ester, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, phosphate buffer solution Deng；It is preferred that deionized water, toluene, chloroform, dichloromethane, 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 be usually alkyl quaternary ammonium ion, alkyl quaternary see ion, the substitution of 1,3- dialkyl group imidazol ion, N- alkyl take 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 aggregation object using deionized water and selecting to be retained, hydrogel can be obtained；Using organic Solvent come prepare dynamic aggregation object and select retained when, organogel can be obtained；It is poly- that dynamic is prepared using oligomer When closing object and selecting to be retained, oligomer swell gel can be obtained；Dynamic aggregation object is prepared using plasticizer and is selected When being retained, plasticizer swell gel can be obtained；Dynamic aggregation object is prepared using ionic liquid and selects to be retained When, ionic liquid swell gel can be obtained.
In above-mentioned preparation method, prepared compound liquid concentration is according to the structure of selected reactant, molecular weight, dissolving Depending on degree and required dispersity, it is not particularly limited, preferred a concentration of 0.1~10mol/L of compound liquid, more preferably For 0.1~1mol/L.
The specific method for preparing hydridization dynamic aggregation object material is stirred using melting, typically by raw material in reactor In be directly stirred or heat melting after be stirred reaction, such mode generally raw material for gas, liquid or fusing point compared with It is used in the case of low solid.In general, hybrid reaction temperature is controlled at 0-200 DEG C, and preferably 25-120 DEG C, more preferable 25-80 DEG C, time control is mixed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mould In tool, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, polymer samples are obtained.
When preparing hydridization dynamic aggregation object material using the method as raw material using compound (IV), compound (V), usually It also needs to be optionally added into a small amount of initiator and obtains dynamic aggregation object in a manner of melt polymerization or gas-phase polymerization to cause polymerization. The method of its used melt polymerization, gas-phase polymerization, is well known to those skilled in the art and widely used polymerization Method can be adjusted according to actual conditions, no longer be developed in details here.
The specific method of hydridization dynamic aggregation object material is mixed with using melting extrusion, be typically add the raw material into it is crowded Go out and carry out extrusion blending reaction in machine, extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can direct tape casting After be cut into suitable dimension, either by obtained extrusion sample carry out it is broken after utilize injection molding machine or moulding press to carry out sample preparation.Note Mould 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, preferably 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.It can incite somebody to action Batten is placed in suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, is placed 0-48h, is obtained final polymerization Object sample.
In the preparation process of hydridization dynamic aggregation object material, selected organoboron compound (I), polyol compound (II), compound (III), compound (IV), compound (V) can flexibly be held at component selections and formula rate, but answer root According to target material performance and the structure of selected compounds, the reactive group number contained and molecular weight carry out reasonably design and Combination.Wherein, the organoboron compound (I) that is added, compound (III), compound (IV), is changed polyol compound (II) It closes object (V) and should ensure that the molar equivalent ratio of functional group and/or other reactive groups in reactant system is in model appropriate It encloses.The glycol primitive and organic boronic primitive contained in organoboron compound (I), polyol compound (II), compound (III) Range of the molar equivalent of functional group than preferably 0.1~10, more preferable 0.3~3 range, more preferable 0.8~1.2 range. When the molar equivalent ratio for the functional group contained in organoboron compound (I), polyol compound (II), compound (III) is close 1:When 1, the dynamic aggregation object that the extent of reaction is high, stability is good can be obtained；When organoboron compound (I), polyol compound (II), the molar equivalent for the functional group contained in compound (III) is than deviateing 1:When 1, then it is preferably dynamic can to obtain dynamic State polymer material.Similarly, when selecting compound (IV), compound (V) to prepare dynamic aggregation object as reactive component, instead It answering the molar equivalent of other reactive groups in objects system than also should be at range appropriate, carrying out other reactions of polymerisation Range of the molar equivalent than preferably 0.1~10 of property group, more preferable 0.3~3 range, more preferable 0.8~1.2 range. In actual fabrication process, those skilled in the art can be adjusted according to actual needs.
Hydridization dynamic aggregation object in the present invention is due to having the cyclic annular organic boric acid ester key of dynamic and side hydrogen bond group shape At supermolecule hydrogen bond so that the dynamic aggregation object obtained have excellent dynamic reversibility and good toughness, pass through conjunction Suitable component selection and formula designs, and material can be applied to military aerospace equipment, functional coating, biological medicine, bio-medical material The fields such as material, the energy, building, bionical, intellectual material, have broad application prospects.
For example, making full use of self-repairability possessed by dynamic aggregation object, can prepare viscous with self-repair function Agent is tied, is applied to the gluing of various types of materials, also can be used as bulletproof glass squeegee；It can also be used for preparing and there is good plasticity simultaneously And the polymer that can recycle reuse blocks sealing elements such as glue and sealing-plug, sealing ring etc., or it is wear-resisting and anti-using preparing Tear taper knob etc.；Based on the dynamic reversibility of cyclic annular organic boronic ester bond and side hydrogen bond, it can design to prepare to have and review one's lessons by oneself The scratch resistant coatings of multiple function are realized and are protected to the long-effective corrosion of basis material to extend the service life of coating；Pass through conjunction Suitable component selection and formula designs, and can prepare polymer gasket or polymer plate with self-repair function, so as to The principle to be healed with mimic biology bulk damage so that material can carry out self-healing to internal or outer damage, eliminate hidden Suffer from, extends the service life of material, huge application potential is shown in the fields such as military project, space flight, electronics, bionical.
For another example the introducing of cyclic annular organic boronic ester bond and supermolecule hydrogen bond so that polymer material is under external force Excellent toughness is reflected, it is hereby achieved that thin polymer film, fiber or plank that toughness is splendid, are widely used in army The fields such as thing, space flight, movement, the energy, building；Also it can be used as shape-memory material, when the external force is removed, material Expect that the deformation generated in loading procedure can be restored；The dilatancy that may be based on dynamic aggregation object, by polymer application It is explosion-proof with fuel oil in recovering the oil, polymer material can also be applied to make the magic effect converted with viscosity flow and high resiliency Toy and body-building material；Based on the dynamic of dynamic aggregation object, in the case where filling conductive filler, polymer composition is led Electrically it is easy to generate external force sensitive response, and then can be used for preparing force snesor.
Hydridization dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
5g diaminomethyl phenyl boric acids compounds is added in three-necked flask (with 2- aminomethyl phenyls boric acid, 1,6- oneself two isocyanides Acid esters is raw material, and both control molar ratio is 2:1, at room temperature reaction be made), 30g polyol compounds (a) (with propylene glycol, 2- methyl-2-propyls [3- (2- Oxyranyles) propyl] carbamate is raw material, and boron trifluoride ether is catalyst, is passed through Cation ring-opening polymerization synthesizes the epoxy propane copolymer that side group carries carbamate groups；Again by itself and acrylic acid, 3- mercaptos Base -1,2-PD is made by esterification, mercaptan-alkene hydrocarbon click addition reactions respectively), 200ml toluene solvants are added, It is heated to 60 DEG C and is stirred dissolving, after mixing 30min, then be added dropwise to 2ml triethylamines, continue to be stirred to react, in reaction process In, solution viscosity constantly rises, and is stirred to react after 3h, is surveyed to the apparent viscosity of polymer fluid using rotational viscometer Examination, wherein test temperature is 25 DEG C, and constant shear rate is 0.1s-1, the apparent viscosity for measuring polymer fluid is 17, 946mPa·s.Hydridization dynamic aggregation logistics body can show apparent dilatancy under shear action, can be applied to and adopt Oily engineering increases the viscosity of displacing phase in Drainage process, to improve oil recovery factor.
Embodiment 2
The PolyTHF of 30g phenyl boric acid bi-end-blockings is added in three-necked flask (using 4- amino phenyl boric acid as raw material, by it PolyTHF with dibromo sealing end is made using potassium carbonate as catalyst by hydrocarbyl reaction), the polyol compound of 3.8g (a) (be catalyst by initiator, triethylamine of AIBN, using 1,3,5- triacryl hexahydro -1,3,5-triazines successively with it is fixed N- [(2- mercaptos ethyl) carbamyl] propionamide of amount, 3- sulfydryl -1,2- propylene glycol pass through mercaptan-alkene hydrocarbon click addition reactions It is made), it is added dropwise to a small amount of BHT antioxidant, after being heated to 120 DEG C of mixing 30min, a small amount of triethylamine is added dropwise to, in nitrogen React 3h under the conditions of gas shielded, then pour into sticky reaction solution in suitable mold, be placed in 80 DEG C of vacuum drying ovens for 24 hours into The further reaction of row, is cooled to is placed at room temperature for 30min later, finally obtain polymer samples colloid, soft surface has Lower melt viscosity can be used as the super hot melt adhesive with self-healing properties.
Embodiment 3
Be added in three-necked flask 3.2g organic boric acid compounds (with vinyl boronic acids, 1,3- dimercaptopropanes for raw material, with AIBN is initiator, triethylamine is catalyst, is made by mercaptan-alkene hydrocarbon click addition reactions), the poly- fourth of 15g glycol sealing end Diene (a) (under DCC, DMAP catalytic action, the end hydroxy butadiene and 2 for being about 4000 using molecular weight, 2- dihydroxymethyls The polybutadiene of glycol sealing end is made by esterification for propionate, then by itself and N- [(2- mercaptos ethyl) carbamyl] propionamide It is made with by thiol-ene click-reactions), the epoxidized soybean oil of 100ml is added, is heated to 60 DEG C and is stirred mixing, stir After mixing mixing 30min, 2ml triethylamines are added, adds 0.5g organobentonites, 0.5g bentonite, continues to be stirred to react 2h, it will be anti- Object is answered to be poured into suitable mold, the 12h that is placed in 60 DEG C of vacuum drying ovens that the reaction was continued is cooled to is placed at room temperature for 30min later, Obtain gelatinous dynamic aggregation object sample.Polymer samples have lower case hardness, can extend with outer force effect. In the present embodiment, the encapsulation process of building filleting or electronic component can be applied to using polymeric articles as sealant.
Embodiment 4
The polyethylene oxide (a) of 24ml boric acid lists sealing end is added in three-necked flask (by vinyl boronic acids and 2- sulfydryl second After alcohol is by thiol-ene click-reactions, using boron trifluoride ether as catalyst, one is utilized after causing epoxyethane ring-expansion polymerization Chloromethanes sealing end is made), 8ml polyol compounds (b) are (with DIETHYLENE GLYCOL and N- [(2- mercaptos ethyl) carbamyl] third Diol monomer 1, using diol monomer 1, ethylene oxide as raw material, boron trifluoride second is made by thiol-ene click-reactions in amide Ether is catalyst, and the polyethylene oxide that side group carries hydrogen bond group is synthesized by cation ring-opening polymerization；Again by it with acrylic acid, 3- sulfydryls -1,2-PD is clicked addition reaction and is made by esterification, thiol-ene respectively), 2ml triethylamines are added dropwise to, It is stirred reaction under the conditions of 80 DEG C, after reacting 4h, is cooled to room temperature, translucent viscous samples, polymer can be obtained Sample has unformed property and lower fusing point, can extend easily under external force, can as tackifier or Viscosity modifier is used.
Embodiment 5
80ml THF solvents are added in the reaction bulb of dried and clean, after leading to nitrogen deoxygenation 1h, 10.8g acid esterifications are added Object is closed (using 5- hexenes ylboronic acid, 3- (allyloxy) -1,2-PD as raw material, using triethylamine as catalyst, in 80 DEG C of conditions Be made by condensation reaction down), 3mg BHT, 0.03g AIBN and 0.68g triethylamines after mixing, be added dropwise to 8.10g 3, 6- dioxa -1,8- octanedithiols, react 4h under the conditions of nitrogen protection, add 15g modified propylenes-isoprene copolymer Object is (with metallocene catalyst rac-CH2(3-t-Bu-Ind)2ZrCl2) catalysis propylene and isoprene copolymer close be made side group contain Propylene-isoprene copolymer of ethenylidene double bond, then itself and N- [(2- mercaptos ethyl) carbamyl] propionamide are passed through Thiol-ene click-reactions are made), the reaction was continued 3h.After reaction, it is cooled to room temperature, can finally obtain having certain viscous The polymeric colloid of degree, can as a kind of binder with selfreparing effect, be applied to rubber, plastic or other material it is viscous Knot.
Embodiment 6
Weighing a certain amount of organoboron compound (a), (using AIBN as initiator, triethylamine is catalyst, by trihydroxy methyl third Alkane three (3-thiopropionate) is logical with quantitative ethyl -5- hexene -1- aminocarbamic acids ester, propylene ylboronic acid diisopropyl ester respectively Thiol-ene click-reactions are crossed to be made) it is dissolved in tetrahydrofuran solvent, it is configured to the solution of 0.3mol/L, and take 20ml molten Liquid is added in the reaction bulb of dried and clean, is added dropwise to 20% a small amount of acetic acid aqueous solution, is stirred evenly for use；It weighs a certain amount of (using glycerine, propylene oxide as raw material, boron trifluoride ether is catalyst to three arm polypropylene oxide (b) of glycol sealing end, is passed through Three arm polypropylene oxide of cation ring-opening polymerization synthesis of hydroxy sealing end, then it is obtained into three arms by esterification with acrylic acid and is gathered Propylene oxide triacrylate, then by its respectively with quantitative N- [(2- mercaptos ethyl) carbamyl] propionamide, 3- sulfydryls -1,2- Propylene glycol is made by thiol-ene click-reactions) it is dissolved in tetrahydrofuran solvent, it is configured to the solution of 0.3mol/L, and It takes 20ml to be uniformly mixed with organic B solution before, is placed in 50 DEG C of water-bath and is stirred reaction 30min, then add Entering 1ml triethylamines, 5wt% shell powder continues after being stirred to react 2h, the polymer solution with certain viscosity is poured into mold, It is placed in 50 DEG C of baking ovens and is dried except solvent, be cooled to be placed at room temperature for 30min later, finally obtain thin polymer film.Polymerization Object film soft texture, after being cut off with blade, section part is slightly heated to fitting to form a film again, has self-repairability, It, can be as Wound care film and applied to medical nursing field using its biocompatibility.
Embodiment 7
The organoboron compound (a) of a certain amount of dissaving structure is taken (using diethanol amine, methyl acrylate as raw material, to synthesize 3- (bis- (2- ethoxys) amino) methyl propionate；Again by it in the form of dropwise addition with trimethylolpropane in Catalyzed by p-Toluenesulfonic Acid Under the conditions of, reacted under the conditions of 115 DEG C and level-one intermediate product be made, then again with 3- (bis- (2- ethoxys) amino) methyl propionate Two level intermediate product is made in reaction, after then utilizing the progress of 3- isocyanide acid propylenes hydroxy-end capped, then with quantitative 4- sulfydryl benzene boron Acid passes through thiol-ene click-reactions and final product is made) it is dissolved in chloroform solvent and is configured to the molten of 0.02mol/L Liquid；A certain amount of polyol compound is taken (to utilize Et (Ind)2ZrCl2/ MAO catalyst system and catalyzings are catalyzed propylene polymerization and ethenylidene are made End group polypropylene, then itself and 3- sulfydryls -1,2-PD are made by thiol-ene click-reactions) dissolve by heating in trichlorine The solution of 0.12mol/L is configured in methane solvent.20ml organoboron compounds solution and polyol compound solution is respectively taken to add Enter into the flask of dried and clean, be stirred 30min, then be added dropwise to a small amount of triethylamine, under 60 DEG C of water-bath conditionals Continue to be stirred to react 2h.After reaction, the apparent viscosity of polymer fluid is tested using rotational viscometer, wherein Test temperature is 25 DEG C, and constant shear rate is 0.1s-1, the apparent viscosity for measuring polymer fluid is 7,400mPas, dynamic Polymer imparts polymer fluid with the effect of " shear thickening ".This polymer solution can be applied to the anti-of flammable liquid Quick-fried, after adding the polymer in a liquid, flammable liquid, since viscosity increases, is not likely to produce winged during stirring use It splashes, to increase safety.
Embodiment 8
Acrylate-phenyl boric acid copolymers of the 20g with side hydrogen bond is added in three-necked flask (by 4- hydroxymethyl benzene boron Sour pinacol ester is reacted with acryloyl chloride is made borate ester acrylate monomer 1；By isocyanates ethyl acrylate and ethamine The acrylate monomer 2 containing urea bond is made in reaction；Using AIBN as initiator, by borate ester acrylate monomer 1 and acrylic acid Ester monomer 2, methyl methacrylate are obtained by free radical polymerization), 200ml ethyl acetate solvents are heated to 50 DEG C and are stirred After mixing dissolving, it is added dropwise to a small amount of 20% acetic acid aqueous solution, it (is to draw with acrylic acid to be slowly added into 6.8g glycol lists terminated polycaprolactone Agent is sent out, stannous octoate is catalyst, causes the polycaprolactone that 6-caprolactone ring-opening polymerisation obtains alkene list sealing end, then by itself and 3- mercaptos For base -1,2-PD using AIBN as initiator, triethylamine is catalyst, is finally produced by thiol-ene click-reactions Object), after being stirred 30min, 2ml triethylamines are added, the Cellulose nanocrystal and 0.3wt% detergent alkylates of 6wt% is added Sodium sulfonate, ultrasonic 20min are heated to 80 DEG C and continue to be stirred to react 2h.After reaction, solvent is sloughed by decompression suction filtration to obtain White residue, obtains dynamic aggregation object solid after being purified, surface can be made uniformly and with certain glossiness It is made art modelling material or art furnishings.
Embodiment 9
Acrylamide-phenyl boric acid-urethane copolymers of the 20g with side hydrogen bond are added in three-necked flask (with different Methyl-cyanate, N- (2- ethoxys) acrylamide are that carbamate monomer is made in raw material reaction；It, will again using AIBN as initiator Acrylamide, 3- acrylamidos phenyl boric acid, carbamate monomer are obtained by RAFT free radical polymerizations), 3.5g seasons penta 4 Alcohol, 120ml deionized waters, be heated to 80 DEG C be stirred 30min after, be added 2ml triethylamines, continue to stir under the conditions of 80 DEG C React 2h.Then 1.5g neopelexes, 0.9g bentonite, 0.5g stearic acid, 0.5g oleic acid is added, then is added wherein 0.6g organobentonites, 0.6g dimethyl silicone polymers, 0.6g dibutyl tin laurates, 50mg light stabilizers 770 continue to add After thermal agitation mixing 2h, the dynamic aggregation object with certain viscosity is obtained, it can be coated on substrate surface, as can selfreparing Coating uses.
Embodiment 10
The boric acid modified silicone oil of addition 30ml (is about with vinyl boronic acids, viscosity in the three-necked flask of dried and clean The end hydrogen-based silicone oil of 6000mPas is raw material, and Si―H addition reaction is carried out under Pt catalytic conditions and is made), 30ml atoleines, 8ml Four arm polysiloxanes (a) (reacted as raw material using isocyanates ethyl acrylate, ethamine and compound 1 be made；With prestox ring four Siloxanes, four (dimethylsilyl bis) silane are raw material, and the concentrated sulfuric acid is catalyst, and it is poly- to synthesize four end hydrogen-baseds by ring-opening polymerisation method Siloxanes, then it is passed through into silicon with quantitative compound 1,3- (allyloxy) -1,2-PD under Pt catalytic conditions respectively Final product is made in addition reaction of hydrogen), 5mg BHT antioxidant, be heated to 90 DEG C be stirred 30min after, be added tri- second of 1.5ml Amine, continuation react 4h under the conditions of 90 DEG C, obtain the polymer samples with larger viscosity, be poured into suitable mold, It is placed in placement 4-6h in 90 DEG C of vacuum drying ovens further to be reacted, is cooled to is placed at room temperature for 30min later, finally obtain Lurid polymer elastomer.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, utilizes drawing It stretches testing machine and carries out extension test, rate of extension 50mm/min, it is 1.52 ± 0.24MPa to measure sample tensile strength, is stretched Modulus is 2.28 ± 0.76MPa, and elongation at break is 1537 ± 395%.Polymer elastomer surface strength is relatively low, has without fixed Type and good heat-resisting moisture resistivity.Breaked sample breaks after section part application stress is placed in 60 DEG C of molds and places 3-4h Face can bond again, have recuperability.It can be using obtained polymer elastomer as a kind of recuperability electronic encapsulation material It uses.
Embodiment 11
Taking a certain amount of dendritic organoboron compound (a), (using DMPA as photoinitiator, ultraviolet light is light source, by three Allyl amine and 1, after level-one intermediate product is made by mercaptan-alkene hydrocarbon click addition reactions in 2- dithioglycols, then with three allyls Base amine continues through mercaptan-alkene hydrocarbon click addition reactions and two level intermediate product is made, and passes through sulphur with 1,2- dithioglycols again later Three-level intermediate product is made in alcohol-alkene click addition reactions, then is reacted with triallylamine and level Four intermediate product is made, finally Pass through mercaptan-alkene hydrocarbon click with quantitative [4- (mercapto methyl) phenyl] boric acid, N- [(2- mercaptos ethyl) carbamyl] propionamide Final product is made in addition reaction) it is dissolved in the solution that 0.1mol/L is configured in toluene solvant.Take 40ml organoboron compounds Solution is added in the reaction bulb of dried and clean, and 3.2g diol compounds (b) are added (with diethylene glycol double methacrylate, 3- mercaptos Base -1,2-PD is raw material, is catalyst by initiator, triethylamine of AIBN, passes through mercaptan-alkene hydrocarbon click addition reactions Be made), the BHT antioxidant of 0.2mg, 0.2g triethylamines, after stirring evenly, react 2h under the conditions of 80 DEG C of nitrogen protections.Later Polymer solution is poured into suitable mold, is placed in 50 DEG C of baking ovens to place and is dried and further reacts for 24 hours, Finally obtain membranaceous polymer samples.It is cut into the dumbbell shape batten of 80.0 × 10.0 × (0.08 ± 0.02) mm sizes, Using cupping machine carry out extension test, rate of extension 50mm/min, measure sample tensile strength be 2.21 ± 0.58MPa, stretch modulus are 4.12 ± 1.00MPa, and elongation at break is 1196 ± 321%.According to QB/T 1130-91 plastics Right-angle tearing method for testing performance produces right angle and carries out film splitting performance test without scarfing type standard sample, measures sample transverse direction Tearing strength is 6.21 ± 1.79MPa, and machine direction tear is 6.68 ± 1.54MPa.Obtained thin polymer film quality is softer, It with certain intensity and toughness, can extend in a certain range, and there is certain tear resistance.Sample breaks it After recycle, place it in 50 DEG C of mold be bonded 2-4h after, can form a film, be reused again, can using its property It is used as a kind of recuperability packaging film.
Embodiment 12
Acrylamide-boric acid copolymers of the 8.0g with side hydrogen bond is weighed in the beaker of dried and clean (with 1- amino second Ylboronic acid, acryloyl chloride are that monomer 1 is made in raw material reaction；It is reacted as raw material using isocyanates ethyl acrylate, ethamine and is made single Body 2；Monomer 1, monomer 2 and N,N-DMAA are obtained into final product by free radical polymerization), 6.5g carries side hydrogen Acrylamide-diol copolymer of key (is reacted as raw material using isocyanates ethyl acrylate, ethamine and monomer 1 is made；By monomer 1, 2,3- dihydroxypropyl acrylate obtain final product with N,N-DMAA by free radical polymerization), and at it Middle addition 100ml ionic liquid 1-butyl-3-methyl imidazolium fluoroform sulphonates, be placed under the conditions of 60 DEG C constantly stir it is molten Solution is added dropwise to the ammonia spirit of a small amount of 1mol/L, is placed in 60 DEG C of water-baths and carries out heating reaction wherein after dissolving completely 1h, adds 1.45g carbon nanotubes, and 0.15g neopelexes add after stirring 30min under the conditions of 60 DEG C The bentonite of 0.08g continues to be stirred hybrid reaction 3h at 60 DEG C.Sticky polymer solution is poured into suitable mold, The 5h that is placed in 50 DEG C of vacuum drying ovens that the reaction was continued, is cooled to is placed at room temperature for 30min later, finally obtain carbon nanotube compound ion Liquid gel polymer with certain elasticity, and can carry out stretching extension, it is made into 80.0 × 10.0 × (2.0~ 4.0) the dumbbell shape batten of mm sizes carries out extension test using cupping machine, and rate of extension 50mm/min measures sample Tensile strength is 2.15 ± 0.72MPa, and stretch modulus is 3.98 ± 1.54MPa, and elongation at break is 682 ± 277%.Use pocket knife After polymer gel is cut off, section part is glued and placed in section after heating 2-3h in 60 DEG C of baking ovens to be bonded again, is embodied Self-healing properties are gone out.It can be this using the dynamic aggregation object gel in embodiment as carbon nanotube composite intelligent Signa Gel The conductivity of Signa Gel can show good response effect as external force changes, and can be sensed as a kind of stress monitoring Device is used, and reflects selfreparing effect.
Embodiment 13
200ml deionized waters are measured in the three-necked flask of dried and clean, and 15g vinyl pyrrolidones-boron is then added Hydrochlorate copolymer (it is reacted as raw material using 4- hydroxy benzenes boric acid sodium salt, acryloyl chloride and borate acrylate monomer is made, then with AIBN is initiator, it is obtained final product with vinyl pyrrolidone by free radical polymerization), 8g polyvinyl alcohol, 8g second (with isocyanates ethyl acrylate, 2-aminopyridine is that monomer 1 is made in raw material reaction to vinyl pyrrolidone-urea groups copolymer；With AIBN is initiator, and monomer 1 and vinyl pyrrolidone are obtained final product by free radical polymerization), heating stirring dissolving Afterwards, continue to be stirred 30min, be added dropwise to the NaOH solution of a small amount of 1mol/L, water bath with thermostatic control reaction 2h under the conditions of being placed in 60 DEG C, After polymer solution has certain viscosity, Fes of the 3.2g Jing Guo 151 surface modification of silane coupling A is added3O4Particle, 1.5g Shellac and 2.0g bentonite, ultrasonic 1min make Fe3O4Particle is uniformly dispersed wherein, and it is anti-to continue water bath with thermostatic control under the conditions of being placed in 60 DEG C Answer 2h.After reaction, the dynamic aggregation object hydrogel for being dispersed with magnetic particle is obtained.Polymer gel sample surfaces are sticky, A degree of stretching can be carried out, there is certain elasticity.After being cut off polymer gel with blade, section is bonded, is set 2-3h is placed in 60 DEG C of baking ovens, gel can bond again.In the present embodiment, obtained magnetic gel has good Deformability and shape memory the deformation such as can extended, shunk or are being bent outside plus under magnetic fields, utilize it Possessed magnetic responsiveness, self-repairability and deformability can be in enzyme or the solid of cell, bio-separation, drug controlled release and biographies Sensor etc. has potential purposes.
Embodiment 14
35ml organic boronics-glycol graft modification silicone oil (a) is added in the reaction bulb of dried and clean (is about with molecular weight 30,000 methyl mercapto silicone oil, two chloroborane of acrylic, (2,3- dihydroxy butylcyclohexyl) methylmethacylate are raw material, DMPA is photoinitiator, under the conditions of ultraviolet light, is made by thiol-ene click-reactions), the grafting of 15ml hydrogen bond groups Modified silicon oil (b) (using ethyl mercaptan and isocyanates ethyl acrylate as raw material, is obtained by the reaction containing thio carbamate groups Acrylate, then by its be about 30,000 with molecular weight methyl mercapto silicone oil using DMPA as photoinitiator, in ultraviolet lighting Under the conditions of penetrating, by thiol-ene click-reactions be made), be heated to 80 DEG C and be uniformly mixed, be added 20% acetic acid it is water-soluble After liquid mixing 30min, then it is added dropwise to the triethylamine of 2ml, continues to be stirred to react.In polymerization process, the viscosity of silicone oil is not It is disconnected to rise, it when it reaches certain viscosity, is poured into suitable mold, is placed in 80 DEG C of vacuum drying ovens that the reaction was continued For 24 hours, it being cooled to later and is placed at room temperature for 30min, finally obtain transparent dynamic aggregation object glue, surface has certain viscosity, And excellent tensile toughness (elongation at break is up to 3000%) is embodied, it slightly heats, breaks after polymer samples are broken The sample split can bond again automatically, can as with selfreparing property rubber adhesive or salvage of casting agent into enforcement With.
Embodiment 15
22g phenyl boric acids modified silicon rubber is weighed (using methyl vinyl silicone rubber, 4- mercaptophenyl boronic acids as raw material, with DMPA As photoinitiator, under the conditions of ultraviolet light, by mercaptan-alkene hydrocarbon click addition reactions be made), 20g glycol modification silicon Rubber is (using methyl vinyl silicone rubber, 3- sulfydryls -1,2-PD as raw material, using DMPA as photoinitiator, in ultraviolet lighting Under the conditions of penetrating, be made by mercaptan-alkene hydrocarbon click addition reactions), 8g hydrogen bond group modified silicon oils (a) are (with cyanuric acid, 6- Chloro- 1- hexenes are raw material, the olefin(e) compound of hydrogen bonds group are obtained by the reaction under potassium carbonate catalysis, then be by itself and molecular weight 20,000 Methyl Hydrogen Polysiloxane Fluid carried out under Pt catalytic conditions Si―H addition reaction be made), 8g white carbons, 8g titanium dioxides, 1.5g tri- It aoxidizes two iron and is added in small-sized internal mixer and be kneaded 30min, after so that additive is sufficiently mixed uniformly with sizing material, take out sizing material, It is heat-treated 1h under the conditions of 120 DEG C.4h is placed in 80 DEG C of vacuum drying ovens later, then in 10MPa forming under the pressure, obtains silicon rubber The dynamic aggregation object material of base.The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into using mold, Using cupping machine carry out extension test, rate of extension 50mm/min, measure sample tensile strength be 2.54 ± 0.76MPa, stretch modulus are 5.37 ± 1.78MPa, and elongation at break is 2171 ± 367%.Dynamic aggregation object material can be Creep is generated under outer force effect, can be stretched on a large scale and not broken, the magic with superpower toughness can be made into Plasticine toy.
Embodiment 16
50ml Methyl Hydrogen Polysiloxane Fluids (molecular weight is about 30,000) are added in the three-necked flask of dried and clean, lead to nitrogen 1h Afterwards, 6.81g boric acid ester compounds (a) are added (using 5- hexenes ylboronic acid, 3- (allyloxy) -1,2-PD as raw material, with three Ethamine is catalyst, is made by condensation reaction under the conditions of 80 DEG C), 3.46g ethyls (2- methyl -4- amylene -1- bases) amino Formic acid esters (b), 2ml 1%Pt (dvs)-xylene solution are heated to 80 DEG C as catalyst, continue under the conditions of nitrogen protection Reaction for 24 hours, finally obtains dynamic aggregation object colloid, soft surface, good toughness can carry out slowly under applied external force It stretches and extends, and obtain super extending effect (elongation at break is up to 5000%).In the present embodiment, dynamic aggregation object can be with It is long-term to keep pellucidity, it can be used polymer samples obtained as the squeegee of bulletproof glass.
Embodiment 17
It weighs 7.28g and is modified EP rubbers (using hexamethylene diamine, ethyl isocyanate as obtained 1- (6- ammonia the hexyl) -3- second of raw material Base urea；Using low molecular weight bibasic ethylene propylene rubber as raw material, using dibenzoyl peroxide as crosslinking agent carry out reaction formed it is small After cluster structure, then in cluster surface grafting maleic anhydride, then using p-methyl benzenesulfonic acid as catalyst, by itself and 4- amino phenyl boric acids Final product is made in pinacol ester, the reaction of 1- (6- ammonia hexyl) -3- ethyl carbamides) it is added in the beaker of dried and clean, pour into 80ml Xylene solvent carry out heating stirring, then be added dropwise to 20% a small amount of acetic acid aqueous solution, after being stirred 30min, add (with 1,9- decadinene, 3- sulfydryls -1,2-PD for raw material, AIBN is initiator to 0.71g diol compounds, and triethylamine is to urge Agent is made by thiol-ene click-reactions), continue to be stirred 30min, adds 1.0mg BHT antioxidant, 1ml tri- Ethamine, continuation react 3h under the conditions of 80 DEG C, obtain sticky polymeric liquid, place it in suitable mold, at 80 DEG C It is placed in vacuum drying oven and removes solvent for 24 hours, be cooled to be placed at room temperature for 30min later, be removed from the molds sample, finally obtain rubber The dynamic aggregation object of shape.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, utilizes tension test Machine carries out extension test, and rate of extension 50mm/min, it is 2.37 ± 0.81MPa to measure sample tensile strength, and stretch modulus is 4.15 ± 1.52MPa, elongation at break is up to 824 ± 198%.Polymer samples not only embody certain intensity, Er Qiebiao Excellent toughness is revealed, glue can be blocked as a kind of waterproof and used；In use, material shows good Good viscoplasticity and excellent hydrolytic resistance.When its surface occurs damaged, by heating can be achieved the healing of breakage from And be molded again, realize the selfreparing and recycling of material.
Embodiment 18
120ml chloroform solvents are poured into the flask of dried and clean, are led to nitrogen and are removed water deoxygenation 1h, 15g benzene boron is then added Acid esters modified polycarbonate (a) (extracts limonene oxide from orange peel, its catalysis with carbon dioxide in beta-diimine zinc is made Carry out polymerisation under, obtain makrolon PLimC, then by it with [4- (mercapto methyl) phenyl] boric acid neopentyl glycol ester, N- [(2- mercaptos ethyl) carbamyl] propionamides are made by thiol-ene click-reactions), 13g glycol modification makrolon (b) (limonene oxide is extracted from orange peel, itself and carbon dioxide are subjected to polymerisation under the catalytic action of beta-diimine zinc, obtained Pass through to makrolon PLimC, then by itself and 3- sulfydryls -1,2-PD, N- [(2- mercaptos ethyl) carbamyl] propionamide Thiol-ene click-reactions are made), after being heated to 60 DEG C of stirring and dissolvings, add 4mg BHT antioxidant, 0.8g triethylamines, The glass micro-fibers and 0.3wt% neopelexes of 5wt%, the reaction was continued under the conditions of nitrogen protection 4h will be mixed later Conjunction liquid is placed in suitable mold the drying in 50 DEG C of vacuum drying ovens and for 24 hours, transparent rigid polymer solid is finally obtained, by it The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made, carries out extension test using cupping machine, stretches Rate is 10mm/min, and it is 11.78 ± 3.36MPa to measure sample tensile strength, and stretch modulus is 26.35 ± 7.04MPa, polymerization Object solid quality is hard, and there is higher mechanical strength and case hardness to be placed in sample with blade after its surface scratch Placed in 80 DEG C of vacuum drying ovens 4-5h cuts can selfreparing, instrument board or recuperability with self-healing properties can be made into Container bottle uses.
Embodiment 19
It is (logical using styrene and 4- vinylphenylboronic acids using AIBN as initiator to weigh 32g phenyl boric acids modified polystyrene Cross free-radical polymerized be made), 1,2,5,6- tetrahydroxy hexanes of 2g, 10g hydrogen bond groups modified polystyrene is (by acrylic acid 2- ammonia Base ethyl ester and carbethoxyl group isocyanates obtain the acrylate monomer of hydrogen bonds group under triethylamine catalysis, then with AIBN For initiator, it is made with styrene by free-radical polymerized) it is added in the beaker of dried and clean, it pours into wherein The toluene of 150ml/n-hexane mixed solvent is heated to 80 DEG C and is stirred after dissolving, is added dropwise to a small amount of triethylamine and continues 4h is reacted, mixed solution, which is placed in suitable mold the drying in 60 DEG C of vacuum drying ovens, later for 24 hours, finally obtains translucent Polymer hard solid, surface is smooth, there is certain glossiness, and hardness and mechanical strength are higher, but without elasticity and toughness. It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, extension test is carried out using cupping machine, Rate of extension is 10mm/min, and it is 6.24 ± 1.52MPa to measure sample tensile strength, and stretch modulus is 14.01 ± 3.11MPa, With blade after its surface scratch, sample is placed in 80 DEG C of vacuum drying ovens place 4-5h cuts can selfreparing, can be made At with self-healing properties hard packing box or optical instrument shell use.
Embodiment 20
The boron modified polynorbornene of a certain amount of halogen is taken (using two chloroborane of vinyl, cyclopentadiene as raw material, to pass through Boron modified norbornene is made in Diels-Alder reactions；After vinylamine is reacted with carbethoxyl group isocyanates, then with ring Pentadiene reacts the norbornene that hydrogen bonds group is made by Diels-Alder；By boron modified norbornene, hydrogen bonds The norbornene of group, using metallocene catalyst/methylaluminoxane as catalyst system and catalyzing, passes through polyaddition reaction with norbornene Final product is made) solution that 0.2mol/L is configured in o-dichlorohenzene solvent is dissolved by heating, therefrom take 50ml to be added to dry In the reaction bulb of dry cleaning, it is added dropwise to a small amount of acetic acid aqueous solution, 30min is mixed.Take the poly- drop ice of a certain amount of glycol modification Piece alkene (using 3- (allyloxy) -1,2-PD, cyclopentadiene as raw material, is reacted by Diels-Alder and glycol modification is made Norbornene；After vinylamine is reacted with carbethoxyl group isocyanates, then with cyclopentadiene pass through the Diels-Alder systems of reacting Obtain the norbornene of hydrogen bonds group；By the norbornene of glycol modification, the norbornene of hydrogen bonds group and norbornene with Metallocene catalyst/methylaluminoxane is catalyst system and catalyzing, and final product is made by polyaddition reaction) it dissolves by heating in neighbour two The solution of 0.2mol/L is configured in chlorobenzene solvent, and in the reaction bulb before therefrom 50ml being taken to be added to, at mixed solution In 80 DEG C of condition of water bath heating, so that mixed liquor is uniformly mixed by being stirred continuously, 4ml triethylamines, 2.0g titanium dioxides is then added Silicon continues to be stirred to react 4h under the conditions of 80 DEG C, then pours into the polymer solution with certain viscosity in suitable mold, It is placed in placement 6h in 80 DEG C of vacuum drying ovens further to be reacted and dried, polymer elastomer material is finally obtained, by it The bulk sample of 20.0 × 20.0 × 20.0mm sizes is made, compression performance test, compression speed are carried out using universal testing machine For 2mm/min, it is 1.12 ± 0.34MPa to measure sample compression intensity.Polymer samples surface is smooth, has good compression forever Long morphotropism, obtained polynorbornene elastomer can be applied to make sole, toy, medical device, it is also possible in vehicle pad It is applied in terms of lining and electrically insulating material.
Embodiment 21
The boric acid ester compound of 5.6g diamino sealing end is weighed (using triethylamine as catalyst, by 4- amino phenyl boric acid and 4- (2- amino-ethyls) benzene -1,2- glycol is made under the conditions of 80 DEG C by condensation reaction), 60g styrene-maleic anhydride copolymers Object, 3.2g1- (6- ammonia hexyl) -3- ethyl carbamides (are reacted as raw material using hexamethylene diamine, ethyl isocyanate and are made), and 0.15g is to toluene sulphur Acid, 1.4g di-n-butyltin dilaurates, 4.2g dioctyl phthalates, 8g foaming agents F141b, 0.2g stearic acid, 0.06g Irgasfos 168,0.12g antioxidant 1010s after mixing, are added to progress mixing blending in small-sized internal mixer, and control mixing Temperature is at 40 DEG C or less.After mixing, sample is taken out, is fitted into compression mould, mold, which is closed, carries out pressurized, heated, molding Temperature is 100~110 DEG C, clamp time 10-15min, pressure 10MPa and is then put into the prefoam blank after demoulding 3h is further reacted and is dried in 100 DEG C of vacuum drying ovens, finally obtains polystyrene based polymers foam sample, by it The bulk sample of 20.0 × 20.0 × 20.0mm sizes is made, compression performance test, compression speed are carried out using universal testing machine For 2mm/min, it is 0.56 ± 0.11MPa to measure sample compression intensity.It is obtained polymer foams light specific gravity, easily molded, It can be utilized by heating be molded again after damaged, it can be as food, the bubble wrap material of precision instrument, craftwork Material uses.
Embodiment 22
The ester modified polybutadiene (a) of 30g boric acid is weighed (with Amino End Group 1,3- polybutadiene, (bromomethyl) boric acid two Isopropyl ester is raw material, is made by hydrocarbyl reaction), 25g polyol compounds (b) are (with diethylene glycol double methacrylate, 3- mercaptos Base -1,2-PD is raw material, is catalyst by initiator, triethylamine of AIBN, passes through mercaptan-alkene hydrocarbon click addition reactions It is made), (using DMPA as photoinitiator, ultraviolet light is light source to 15g branched polybutadiene rubber (c), by N- [(2- mercaptos ethyl) Carbamyl] propionamide with end amido polybutadiene by thiol-ene click-reactions be made) after mixing, be added to small After being kneaded 20min in type mixer, 5g carbon blacks, 2g Graphene powders, 0.05g barium stearates, 0.15g stearic acid is added and continues to be kneaded 20min.It takes out the material after being kneaded to be cooled down, is placed in twin-roll machine and suppresses flakiness, cooled down at room temperature, cut-parts, Polymer flake obtained is taken out, is dipped in 90 DEG C of water-baths and is crosslinked, be subsequently placed in 80 DEG C of vacuum drying ovens place 6h into The further reaction of row and dry, finally obtains the dynamic aggregation object crosslinking rubber of polybutadiene-base, it is made into 80.0 × The dumbbell shape batten of 10.0 × (2.0~4.0) mm sizes carries out extension test, rate of extension 50mm/ using cupping machine Min, it is 2.74 ± 0.88MPa to measure sample tensile strength, and stretch modulus is 4.17 ± 1.28MPa, elongation at break 1274 ± 351%.Polymer rubber has good suppleness, can be extended on a large scale under external force and not broken, Good tensile toughness is embodied.In addition, polymer rubber also has good mouldability, modeling can be filled under external force Shape.After two pieces of polymer rubber piece overlapping pressures, it is placed in 60 DEG C of vacuum drying ovens and places 4-5h, two pieces of sheet rubbers can bond It is difficult to separate.Due to being filled with graphene in polymeric matrix, while conductive, conductivity also can be with The variation of external force generates sensitive response, can be used for preparing force snesor.
Embodiment 23
Weigh 28g phenyl boric acid graft modifications butyl rubber (using brombutyl, 4- mercaptophenyl boronic acids as raw material, with DMPA is as photoinitiator, under the conditions of ultraviolet light, is made by mercaptan-alkene hydrocarbon click addition reactions), 27g glycol connects Branch modified butyl rubber is (using brombutyl, 3- sulfydryls -1,2-PD as raw material, using DMPA as photoinitiator, in purple Under the conditions of outer light irradiation, it is made by mercaptan-alkene hydrocarbon click addition reactions), 15g hydrogen bond group graft modifications butyl rubber (with Brombutyl, N- [(2- mercaptoethyls) carbamyl] propionamide are raw material, using DMPA as photoinitiator, in ultraviolet light Under irradiation condition, it is made by mercaptan-alkene hydrocarbon click addition reactions) after mixing, it is added in small-sized internal mixer and is kneaded After 20min, 5g white carbons, 6g titanium dioxides, 0.05g barium stearates, 0.15g stearic acid is added and continues to be kneaded 20min.It takes out and is kneaded Material afterwards is cooled down, and is placed in twin-roll machine and is suppressed flakiness, is cooled down at room temperature, cut-parts, by polymer obtained Thin slice takes out, and is placed in placement 4h in 80 DEG C of vacuum drying ovens and is further reacted and dried, finally obtains and stretched with certain The dynamic aggregation object rubber of intensity can carry out stretching on a large scale and extend under external force, and elongation at break is reachable 2000%.In addition, polymer has certain surface viscosity, after two panels polymer flake overlapping pressure, it is placed in 60 DEG C of vacuum 4-5h is placed in baking oven, two plate sheets can bond and be difficult to tear.It can be blocked this polymer material as pipeline or metope Glue uses, and can embody good caking property, self-repairability and toughness.
Embodiment 24
It weighs 38g boric acid graft modifications polyvinyl chloride and (1- amino-ethyls boric acid and polyvinyl chloride is passed through into graft reaction system ), 42g glycol graft modifications polyvinyl chloride (instead by grafting by 2- (4- aminobutyls) propane -1,3- glycol and polyvinyl chloride Should be made), 20g hydrogen bond group graft modifications polyvinyl chloride (reacts as raw material using hexamethylene diamine, ethyl isocyanate and 1- (6- ammonia is made Hexyl) -3- ethyl carbamides, then it is made with polyvinyl chloride by graft reaction), 20g o-phthalic acid dibutyl esters, 10g MBS Toughener, 1g stearic acid, 0.1g irgasfos 168s, 0.2g antioxidant 1010s, 0.2g di-n-butyltin dilaurates, 0.5g diformazans Base silicone oil after mixing, is added in small-sized extruder and carries out extrusion blending, and extrusion temperature is 120-150 DEG C, and what is obtained squeezes Go out after batten is granulated, carries out sample preparation using small injecting machine, injection temperature is 130-160 DEG C, then by sample obtained Item is placed in mold, and 6h is placed under the conditions of 100-120 DEG C of nitrogen protection, finally obtains the polyvinyl chloride-based dynamic aggregation of toughening Object sample.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, is drawn using cupping machine Stretching test, rate of extension 50mm/min, it is 11.24 ± 3.56MPa to measure sample tensile strength, stretch modulus is 17.28 ± 3.48MPa, elongation at break are 1043 ± 368%, and polymer samples have certain mechanical strength, and show good soft Toughness can be stretched largely.In addition, product obtained also has good plasticity, it can be according to of different shapes Mold is shaped to the polymeric articles of different appearances.In the present embodiment, polymer samples can be made to external-cover-type hose or sky Gas sebific duct uses, can be so that slight crack reparation, carries out recycling repetition by heating under the conditions of 100 DEG C after it slight crack occurs It utilizes.
Embodiment 25
The boric acid ester compound of 2.7g diamino sealing end is weighed (using triethylamine as catalyst, by 4- (amino methyl) benzene boron It is made by condensation reaction under the conditions of 80 DEG C with 2- (4- aminobutyls) propane -1,3- glycol after sour pinacol ester hydrolysis), 1.4g 6- amino -2- deracils, 50g maleic anhydride grafted PPs (using cumyl peroxide as initiator, are used Modified by maleic acid anhydride graft low-molecular-weight polypropylene), the BHT antioxidant of 20mg is added in the three-necked flask of dried and clean, Be heated under the conditions of nitrogen protection 150 DEG C carry out melting be stirred 1h, then be added 0.24g p-methyl benzenesulfonic acid, 1.0g plasticising Agent DOP, 0.25g dimethicone, 5.0g talcum powder, the reaction was continued under the conditions of nitrogen protection 3h.It is suitable to be poured into later Mold in, under the conditions of 120 DEG C using moulding press carry out compression molding, be cooled to be placed at room temperature for 30min later, finally obtain Block-like polypropylene base polymer sample.Polymer samples have certain surface gloss, and case hardness is relatively low, can be in external force Stretching extension is carried out under effect.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, utilizes stretching Testing machine carries out extension test, and rate of extension 50mm/min, it is 7.02 ± 2.14MPa, stretching die to measure sample tensile strength Amount is 12.56 ± 3.79MPa, and elongation at break is 712 ± 201%.After cut being carried out with blade on polymer samples surface, It is placed in 110 DEG C of molds, cut can selfreparing (being may be selected during this to carrying out slightly soaking at cut) after placing 6-8h.This Polypropylene-base dynamic aggregation object material in embodiment can be used as a kind of recuperability gasket, be used for precision instrument or electronics The sealing of product can also be repaired when its surface is cracked or damaged by heating.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every 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 (16)

1. a kind of hydridization dynamic aggregation object, which is characterized in that it contains cyclic annular organic boronic ester bond and is joined by side hydrogen bond group With the supermolecule hydrogen bond of formation；Wherein, the cyclic annular organic boronic ester bond and supermolecule hydrogen bond are as the poly- of dynamic aggregation object It closes linking point or crosslinking linking point or exists simultaneously as polymerization linking point and crosslinking linking point, be to be formed or be maintained The necessary condition of dynamic aggregation object structure；
Wherein, the cyclic annular organic boronic ester bond, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure need to be connected with a carbon atom by boron carbon key, and at least one organic group It is keyed in boron atom by the boron carbon；Indicate aromatic ring, and former containing two adjacent carbon on aromatic ring Son is located in the five-membered ring or hexatomic ring in cyclic annular organic boronic ester bond；
Wherein, the side hydrogen bond group, side group, side chain on polymeric chain independently of the cyclic annular organic boronic ester bond And at least one on the multilevel hierarchy of side group, side chain.
2. hydridization dynamic aggregation object according to claim 1, which is characterized in that the side hydrogen bond group comprising side Base hydrogen bond group and side chain skeleton hydrogen bond group contain following any or several constituents：
Wherein, W is selected from oxygen atom, sulphur atom；X is selected from oxygen atom, sulphur atom, nitrogen-atoms；Wherein, a is the D being connected with X atoms Number；When X is selected from oxygen atom or sulphur atom, a=0, D is not present；When X be selected from nitrogen-atoms when, a=1, D be selected from hydrogen atom, The small molecule alkyl of heteroatom group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；I is Divalent linking group is no more than divalent small molecule alkyl, the molecule of 1000Da selected from singly-bound, hetero atom linker, molecular weight Diatomic polymer chain residue of the amount more than 1000Da；Q is end group, is no more than selected from hydrogen atom, heteroatom group, molecular weight Small molecule alkyl, the molecular weight of 1000Da are more than the polymer chain residue of 1000Da；3, the cyclic structure in 6 is to contain at least one The nonaro-maticity or armaticity nitrogen heterocycle perssad of a N-H keys, and at least there are two ring member nitrogen atoms be nitrogen-atoms, cyclic structure at Annular atom is each independently carbon atom, nitrogen-atoms or other hetero atoms.
3. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object also contains master Chain backbone hydrogen bond group contains following constituent：
4. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object is non-crosslinked Structure, wherein the degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, by oversubscription by cyclic annular organic boronic ester bond Sub- hydrogen bond be formed by the degree of cross linking of supermolecule hydrogen bond crosslinks in its gel point hereinafter, and the sum of degree of cross linking of the two be less than gel Point.
5. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object is that crosslinking is tied Structure, wherein the degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, by supermolecule by cyclic annular organic boronic ester bond Hydrogen bond be formed by the degree of cross linking of supermolecule hydrogen bond crosslinks in its gel point hereinafter, and the sum of degree of cross linking of the two gel point with On.
6. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object is that crosslinking is tied Structure, wherein the degree of cross linking of dynamic covalent cross-linking is formed by its gel point hereinafter, by supermolecule by cyclic annular organic boronic ester bond Hydrogen bond is formed by the degree of cross linking of supermolecule hydrogen bond crosslinks more than its gel point.
7. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object is that crosslinking is tied Structure, wherein the degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point by cyclic annular organic boronic ester bond, by supermolecule Hydrogen bond is formed by the degree of cross linking of supermolecule hydrogen bond crosslinks below its gel point.
8. hydridization dynamic aggregation object according to claim 1, which is characterized in that the hydridization dynamic aggregation object is that crosslinking is tied Structure, wherein the degree of cross linking of dynamic covalent cross-linking is formed by more than its gel point by cyclic annular organic boronic ester bond, by supermolecule Hydrogen bond is formed by the degree of cross linking of supermolecule hydrogen bond crosslinks more than its gel point.
9. the hydridization dynamic aggregation object according to any one of claim 4 to 8, which is characterized in that described to be had by ring-type Machine boric acid ester bond is formed by dynamic covalent cross-linking and described be formed by supermolecule hydrogen bond crosslinks by supermolecule hydrogen bond and be in In same polymer chain or same polymer network structure, or it is in different polymer chain or different poly- independently of each other In polymeric network structure.
10. the hydridization dynamic aggregation object according to claim 1, any one of 4 to 8, which is characterized in that the ring-type has Machine boric acid ester bond is generated by organic boronic primitive and glycol elementary reaction；Wherein, the organic boronic primitive, is selected from Organic boron acidic group, organic boronic ester group, organic boronic alkali, organic boron alkylhalide group；The glycol primitive is selected from 1,2- bis- Alcohol primitive, adjacent diphenol primitive, 1,3- glycol primitive, 2- hydroxymethyl phenol primitives.
11. hydridization dynamic aggregation object according to claim 10, which is characterized in that the organic boronic primitive, with Aminomethyl phenyl group is connected to form aminomethyl phenyl boric acid primitive, has the following structure：
Wherein, A is organic boronic primitive.
12. hydridization dynamic aggregation object according to claim 1, which is characterized in that it is carried out at least with following compound Formula combination is reacted as raw material obtains hydridization dynamic aggregation object：
Organoboron compound (I) containing organic boronic primitive；Polyol compound (II) containing glycol primitive；Contain simultaneously The compound (III) of organic boronic primitive and glycol primitive；Contain cyclic annular organic boronic ester bond and other reactive groups Compound (IV)；Without containing organic boronic primitive, glycol primitive and cyclic annular organic boronic ester bond but contain other reactive bases The compound (V) of group；Wherein, organoboron compound (I), polyol compound (II) and compound (V) be not separately as raw material Prepare dynamic aggregation object material.
13. hydridization dynamic aggregation object according to claim 12, which is characterized in that constitute hydridization dynamic aggregation object composition Recipe ingredient further include it is following any or appoint it is several can additive：Auxiliary agent, filler；
Wherein, addible auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, toughener, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, emulsifier, dispersant, Colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent；
Wherein, addible filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.
14. hydridization dynamic aggregation object according to claim 1, which is characterized in that hydridization dynamic aggregation object and its composition and Polymer chain topological structure in material composition is selected from line style, ring-type, branched, cluster, crosslinking and combinations thereof form.
15. the hydridization dynamic aggregation object according to claim 1,4 to 8,12, any one of 14, which is characterized in that described miscellaneous Change the form of dynamic aggregation object and its composition with following any：Solution, gel, cream, glue, elastomer, is commonly consolidated lotion Body, foamed material.
16. the hydridization dynamic aggregation object according to claim 1,4 to 8,12, any one of 14, which is characterized in that it is applied In self-repairability coating, self-repairability plank, self-repairability binder, sealing material, tough elastomer material, squeegee, toy, shape Shape memory material, force snesor.
CN201710055981.3A 2017-01-25 2017-01-25 A kind of hydridization dynamic aggregation object and its application Pending CN108341943A (en)

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