CN108359100A

CN108359100A - A kind of dynamic covalent polymer and its application

Info

Publication number: CN108359100A
Application number: CN201710056037.XA
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen iron cloth Mstar Technology Ltd.
Priority date: 2017-01-25
Filing date: 2017-01-25
Publication date: 2018-08-03
Also published as: WO2018137504A1

Abstract

The invention discloses a kind of dynamic covalent polymer, it includes there is a dynamic covalently inorganic boric acid estersil key, and the connected linker of the silicon atom in inorganic boric acid estersil keys wherein different from least two contains the carbon atom on dynamic covalent polymer chain.The dynamic covalent polymer has strong dynamic reversibility and energy dissipation because containing inorganic boric acid estersil key, and the functional characteristics such as stimulating responsive, self-repairability are embodied, it has a wide range of applications in fields such as athletic protective, functional coating, biomimetic materials.

Description

A kind of dynamic covalent polymer and its application

Technical field

The present invention relates to intelligent polymer fields, and in particular to a kind of dynamic covalent polymer being made of dynamic covalent bond And its application.

Background technology

Traditional polymer is generally made of common covalent bond, and common covalent bond is due to higher bond energy and thermostabilization Property, therefore polymer is also lacking dynamic with good stability and mechanical performance while.Dynamic aggregation object is then by moving The novel polymeric system of one kind of state formation of chemical bond.According to the difference of the dynamic chemical key in dynamic aggregation object, dynamic is poly- Conjunction object can be divided into the physical dynamic aggregation object based on supermolecular mechanism power and the covalent type dynamic based on dynamic covalent bond is poly- Close object.By the covalent type dynamic aggregation object of dynamic reversible covalent bond formation, due to particularity possessed by dynamic reversible covalent bond Matter, it may have outstanding feature.

Dynamic covalent bond is a kind of chemical bond that controllable reversible reaction can occur under certain condition, it is a kind of than non- Covalent bond is stablized, relatively weak covalent bond, is broken by changing extraneous condition or the dynamic of covalent bond spontaneously may be implemented It splits and is formed.Dynamic covalent bond is introduced into polymer, is a kind of feasible method forming novel dynamic aggregation object.But common is dynamic State covalent bond such as Deere think of-Alder reaction product, oxynitrides etc. generally requires to be broken at high temperature, and Side reaction is serious.How to obtain that dynamic property is strong and controllable, system that have a wide range of application, is then still a difficulty of the prior art Topic.

Invention content

The present invention is directed to above-mentioned background, provides a kind of dynamic covalent polymer, dynamic covalent polymer performance Go out excellent dynamic reversibility, and reflect stimulating responsive, plasticity, self-repairability, recuperability, can re-workability etc. Functional characteristic.

The present invention is achieved by following technical solution：

A kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B Atom is connect with three-O-, and wherein former from the different Si in at least two B-O-Si dynamic covalent bonds based on different B atoms Contain on dynamic covalent polymer main chain backbone containing linker L, the linker L in the linker that son is connected Carbon atom.

A kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B Atom is connect with three-O-, and wherein former from the different Si in at least two B-O-Si dynamic covalent bonds based on different B atoms The linker that son is connected is linker L, and the linker L contains the original of the carbon on dynamic covalent polymer main chain backbone Son.

A kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B Atom is connect with three-O-, and the arbitrary difference Si atom phases in B-O-Si dynamic covalent bonds wherein different from least two The linker of connection is that linker L, the linker L contain the carbon atom on dynamic covalent polymer main chain backbone.

A kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B Atom is connect with three-O-, and wherein from Si atoms are connected in arbitrary different B-O-Si dynamic covalent bonds arbitrary divalent And its above linker of divalent is linker L, the linker L contains the original of the carbon on dynamic covalent polymer main chain backbone Son.

Wherein, the linker L can be the connection containing carbon atom on the skeleton of low molecular weight or high molecular weight Base, preferably molecular weight are more than the macromolecule linker of 1000Da, and the amount of carbon atom contained on its more preferable skeleton is not less than 20 molecular weight is more than the macromolecule linker of 1000Da.Also contain optional hetero atom and/or can on the linker L skeletons With the Elements Atom of formation element organic group.The linker L can have any appropriate topological structure, including but not limited to line Type, ring-type (including but not limited to monocycle, polycyclic, nested rings, bridged ring), branched (including but not limited to star-like, H-type, combed, tree It is dendritic, hyperbranched), two and three dimensions cluster, and the above structure random suitable combination.The linker L can be homopolymerization Object can also be copolymer.The linker L can have any one or more glass transition temperatures.

According to the embodiment of the present invention, different linker L can be contained in a dynamic covalent polymer；Except connection Outside base L, other linkers of part can also be contained and connect the different Si atoms in different B-O-Si, preferably (poly-) siloxanes； Other described linkers can also have any appropriate topological structure.

In heretofore described dynamic covalent polymer, also optionally contain Inorganic Boron oxygen boron key (B-O-B).

Also include optionally supermolecule hydrogen bond action in heretofore described dynamic covalent polymer or its composition, Wherein, supermolecule hydrogen bond action can be/the non-crosslinked effect of intramolecular (cyclic in chain) and/or interchain/intermolecular cross-linking in chain Effect and/or interchain/intermolecular non-crosslinked effect (polymerization).

In embodiments of the present invention, the form of the dynamic covalent polymer or its composition can be solution, breast Liquid, cream, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, Ionic liquid swell gel), foam etc..

In embodiments of the present invention, dynamic covalent polymer is added while property is also an option that in preparation process certain The other polymers that can add/use, auxiliary agent, filler are blended to collectively constitute dynamic covalent polymer.

The present invention also provides a kind of methods of energy-absorbing, which is characterized in that provides a kind of dynamic covalent polymer and is made with it Energy-absorbing is carried out for energy-absorbing material, wherein containing B-O-Si dynamic covalent bonds, wherein any one B in the dynamic covalent polymer Atom is connect with three-O-, and wherein former from the different Si in at least two B-O-Si dynamic covalent bonds based on different B atoms Contain on dynamic covalent polymer main chain backbone containing linker L, the linker L in the linker that son is connected Carbon atom.

In embodiments of the present invention, the dynamic covalent polymer performance is adjustable on a large scale, has wide answer Specifically it can be applied to foreground and make damper, padded coaming, acoustic material, deadener, defense of resistance to impact It is material, athletic protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, shellproof The products such as glass sandwich glue, toughness material, shape-memory material, toy.

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

(1) in the present invention, carbon atom, namely at least portion are carried in the linker between at least partly inorganic boric acid estersil key It is that can be given full play to the advantages of containing carbochain polymer, including but not limited to chemical constitution is enriched, opened up containing carbochain to divide polymer chain It is abundant to flutter structure-rich, performance, specific dynamic covalent polymer can be createed, than the freedom that the prior art has bigger Degree has more superior performances and wider array of purposes than current material.

(2) use the optional Inorganic Boron oxygen boron key of inorganic boric acid estersil key and part as dynamic covalent bond structure in the present invention A kind of dynamic covalent polymer is built, and optionally contains hydrogen bond action, takes full advantage of inorganic boric acid estersil key and supermolecule hydrogen The dynamic of key obtains the dynamic covalent polymer with specific performances such as quick selfreparing, the responses of sensitive stress/strain.With Supermolecule polymer is compared, which has stronger dynamic key bond energy and different stimulating responsives, shows Go out specificity.Due in the dynamic covalent polymer be not present common covalent cross-linking, material can completely selfreparing, it is moulding, return It receives and reprocesses.

(3) present invention in dynamic covalent polymer structure-rich, performance is various, contained by the covalent component of dynamic and Supermolecule component has Modulatory character.By adjusting in raw material compound functional group number, molecular structure, molecular weight and/or It is introduced in raw material compound with reactive group, the group of promotion dynamic, with functional group and/or adjustment original The parameters such as material composition, can prepare the dynamic covalent polymer with different structure, to make dynamic covalent polymer embody Abundant different performance, meets the application demand of different occasions.

(4) dynamic response of dynamic reversible key is strong in dynamic covalent polymer, dynamic response mild condition.Compared to existing Other dynamic covalent systems having, the present invention take full advantage of inorganic boric acid estersil key with good thermal stability and height Dynamic reversibility, can without catalyst, without high temperature, illumination or specific pH under conditions of realize dynamic covalent polymer conjunction At and dynamic reversibility also reduce the limitation of use environment while improving preparation efficiency, extend polymer Application range.In addition, by optionally controlling other conditions (auxiliary agent, adjustment reaction temperature is such as added), it can be suitable In the environment of, accelerates or be quenched dynamic covalent chemical balance, be at required state, this is in existing supramolecular chemistry And more difficult inside dynamic covalent systems accomplish.

(5) dynamic covalent polymer reflects functional characteristic.By adjusting the dynamic component in dynamic covalent polymer, Polymeric acceptor can be made to reveal stimulating responsive and dilatancy, polymer can be under the environmental stimulis such as external force, temperature, pH, illumination It makes a response, changes oneself state.The inorganic boric acid estersil key and supermolecule hydrogen bond of dynamic reversible can pass through after fracture Change external condition and re-start bonding, so that material has the functional characteristics such as plasticity, self-repairability, extends carbon containing While chain polymerization object service life, but also it can be applied to certain special dimensions.

Specific implementation mode

In an embodiment of the invention, a kind of dynamic covalent polymer is provided, which is characterized in that wherein contain B- O-Si dynamic covalent bonds, wherein any one B atom are connect with three-O-, and wherein from least two based on different B atoms Contain place containing linker L, the linker L in the linker that different Si atoms in B-O-Si dynamic covalent bonds are connected Carbon atom on dynamic covalent polymer main chain backbone.

In yet another embodiment of the present invention, a kind of dynamic covalent polymer is provided, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B atom are connect with three-O-, and are wherein based on different B atoms from least two B-O-Si dynamic covalent bonds in the linker that is connected of different Si atoms be linker L, the linker L, which contains, to be in Carbon atom on dynamic covalent polymer main chain backbone.

In yet another embodiment of the present invention, a kind of dynamic covalent polymer is provided, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B atom is connect with three-O-, and B-O-Si wherein different from least two The linker that arbitrary difference Si atoms in dynamic covalent bond are connected is linker L, and the linker L contains in dynamic altogether Carbon atom on valence main polymer chain skeleton.

In yet another embodiment of the present invention, a kind of dynamic covalent polymer is provided, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B atom are connect with three-O-, and wherein from arbitrary different B-O-Si dynamics The arbitrary divalent and its above linker of divalent that Si atoms are connected in covalent bond are linker L, and the linker L, which contains, to be in Carbon atom on dynamic covalent polymer main chain backbone.

Linker L described in the embodiments of the present invention can be the skeleton of low molecular weight or high molecular weight On the linker containing carbon atom, preferably molecular weight be more than 1000Da macromolecule linker, more preferably contain on skeleton Amount of carbon atom not less than 20 molecular weight be more than 1000Da macromolecule linker.Also contain on the linker L skeletons Optional hetero atom and/or can be with the Elements Atom of formation element organic group, wherein the hetero atom optionally contained can be appointed It anticipates suitable hetero atom, including but not limited to O, N, S；The Elements Atom optionally contained can be any appropriate pantogen Son, including but not limited to P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir.It is preferred that linker L by carbon atom directly and B-O-Si The Si atoms of key are connected, and can not only obtain the dynamic of B-O-Si keys, but also can maximally utilise carbon atoms connection The performance of base L.The linker L can have an any appropriate topological structure, and including but not limited to line style, ring-type be not (including but Be limited to monocycle, polycyclic, nested rings, bridged ring), branched (including but not limited to star-like, H-type, combed, dendroid, hyperbranched), two dimension With three-dimensional cluster, and the random suitable combination of the above structure, even with common covalent cross-linking particle (including fiber and Sheet-like particle).The linker L can be homopolymer, can also be copolymer.There are glass transition temperatures by the linker L When spending, there can be any one or more glass transition temperatures；If its glass transition temperature is higher than room temperature, can assign dynamic The better rigidity of state covalent polymer and modulus；If being less than room temperature, the better flexibility of dynamic copolymers, extensibility can be assigned And plasticity.The linker L is preferably alkyl, polyolefin-based, polyether-based, polyester base, polyurethane, polyureas base, polysulfide generation Amine ester group, polyacrylic acid ester group, polyacrylamide base, makrolon base, polyethers sulfuryl, polyarylsulfone (PAS) base, polyether-ether-ketone base, polyamides Imido grpup, polyamide-based, polyamine group, polyphenyl ether, polyphenylene sulfide ether, polyphenyl sulfuryl, but the present invention is not limited only to this.According to this The embodiment of invention can contain different linker L in one dynamic covalent polymer.

In the present invention, the ratio of linker L is higher, can more play the performance of linker L, such as a wide range of optional glass Glass transition temperature, mechanical property, chemical property, optical property, printing performance etc..It is preferred that in linker L covalently in dynamic On polymer backbone the sum of carbon atom and hetero atom account for all atoms on the dynamic covalent polymer skeleton ratio it is not low In 50mol%, more desirably not less than 80mol%.Containing more a high proportion of carbon atom and hetero atom, carbon containing linker can be more played The performance of L.

In the present invention, the linker can also be any other suitable linker in addition to for linker L, including But it is not limited to element linker, miscellaneous element linker；Wherein element linker refers to that linker skeleton is made of Elements Atom, Miscellaneous element linker refers to that linker skeleton is made of hetero atom and Elements Atom.Other linkers preferably (poly-) siloxanes, Including cross-linked silica, most preferably polysiloxanes；Other described linkers can also have an any appropriate topological structure, and one Other different linkers can be contained in a dynamic covalent polymer.

According to the embodiment of the present invention, in the dynamic covalent polymer also include optionally Inorganic Boron oxygen boron key (B-O-B)。

Term " polymerization " used reaction is propagation process/effect of chain in the present invention, including reactant by polycondensation plus The process of product of the reaction formations such as poly-, the ring-opening polymerisation synthesis with higher molecular weight.Among these, reactant is typically The monomer of polymerizing power (can spontaneously be polymerize, or can be polymerize in initiator or outside plus under capable of acting on), The compounds such as oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds or two kinds with The product that upper reactant is polymerize is known as copolymer.It should be pointed out that " polymerization " in the present invention, packet The linear growth process of the chain containing reactant molecule includes the branched process of reactant molecule chain, including reactant molecule chain at Ring process also includes the cross-linking process of reactant molecule chain.

Term " crosslinking " used reaction in the present invention generally refers to lead between reactant molecule and/or in reactant molecule It crosses the chemistry of covalent bond and/or hydrogen bond supramolecular chemistry connects to be formed with two-dimentional, three-dimensional cluster and and then form three-dimensional infinitely The process of reticular pattern structured product.In cross-linking process, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, gradually Cluster (can be two dimension or three-dimensional) is formed, developing deeply is three-dimensional infinite network.Unless stated otherwise, the crosslinking in the present invention Refer in particular to the three-dimensional infinite network structure of gel point or more (containing, similarly hereinafter), non-crosslinked includes line style, branched, cyclic annular, two-dimentional cluster and solidifying Glue point three-dimensional cluster structure isogel point below structure below.

Heretofore described " gel point ", expression is reactant in cross-linking process, and viscosity is uprushed, and starts to coagulate Gelatinization phenomenon reaches reflecting point when a three-dimensional infinite network, also referred to as percolation threshold for the first time.Friendship more than gel point There is co-product three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer architecture；In solidifying Glue point cross-linking products below are only loose link structure, form three-dimensional infinite network structure, are only locally lying in A small amount of three-dimensional net structure, and it is not belonging to the cross-linked network that can constitute an entirety across entire polymer architecture.

Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key (is generally not more than 100 DEG C) under typical temperature and (is generally less than 1 day) more difficult be broken in the usual time comprising But it is 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..

" the dynamic covalent bond " described in embodiments of the present invention, refer to inorganic boric acid estersil key (B-O-Si) and Optional Inorganic Boron oxygen boron key (B-O-B).It should be pointed out that in embodiments of the present invention, Inorganic Boron oxygen boron key can root It is adjusted and controls according to the selection and recipe ratio of reaction mass.

In the present invention, the dynamic covalent polymer molecule that the dynamic covalent polymer is included its can have one Kind or a variety of any appropriate topological structures, including but not limited to line style, ring-type (include but not limited to monocycle, polycyclic, nested Ring, bridged ring), branched (including but not limited to starlike, H-type, pectination, dendroid, hyperbranched), two-dimensional/three-dimensional cluster, three-dimensional unlimited Network cross-linked structure and combinations of the above form.Polymer chain can have side group, side chain, branch, and side group, side chain, branch Chain can continue, with side group, side chain, branch, can also have multilevel hierarchy.

In the present invention, the cross-linked network in the dynamic covalent polymer and its composition is dynamic covalent cross-linking net Network, once the effect dissociation of dynamic covalent cross-linking, cross-linked structure just dissociate.But it is not excluded for general to have existing for filling forms The crosslinked particle of valence (including fiber and sheet-like particle) in all.The dynamic covalent cross-linking namely be based on inorganic boric acid estersil key (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) realize crosslinking.In embodiments of the present invention, the dynamic is total Valence link can also exist in noncrosslinking polymer/small molecule.Therefore, the dynamic covalent polymer can be that dynamic is covalent Cross-linked polymer, or the polymer of non-dynamic covalent cross-linking.

In the present invention, the dynamic of Inorganic Boron oxygen boron key is weaker than inorganic boric acid estersil key.It is inorganic by adjusting and controlling The quantity and ratio of boron oxygen boron key can obtain the adjustable dynamic covalent polymer of dynamic.

In embodiments of the present invention, the dynamic covalent bond is formed dynamic except being present on main polymer chain skeleton Except the covalent polymerized/cross-linked of state, it can also exist simultaneously in the side group and/or side chain and/or branch of main chain and/or bifurcated chain And its in the side group and/or side chain and/or branch and/or bifurcated chain of next stage and/or lower multistage.The present invention is also not excluded for simultaneously Contain dynamic covalent bond in the side group of polymer chain and/or end group.Wherein there was only the dynamic covalent bond on cross-linked network skeleton Dynamic covalent cross-linking could be constituted.Under suitable conditions, the dynamic covalent bond of any position all may be used in dynamic covalent polymer To participate in dynamic reversible exchange.In the cross-linked network structure of dynamic covalent polymer, the dynamic for constituting dynamic covalent cross-linking is total Once dissociating, total effective degree of cross linking of polymeric system will reduce valence link.Any two it is nearest contain inorganic boric acid estersil Inorganic boric acid estersil bond number amount (ratio for accounting for all keys) between the crosslinking points of key on skeleton there is no limit, can be one or Person is multiple, preferably contain only there are one.When there are one containing only, dynamic covalent polymeric structure is more regular, and dynamic is more controllable.

Also include optionally supermolecule hydrogen bond action in heretofore described dynamic covalent polymer and its composition, Wherein, supermolecule hydrogen bond action can be/the non-crosslinked effect of intramolecular (in chain/intramolecular cyclization) and/or interchain/molecule in chain Between crosslinked action and/or interchain/intermolecular non-crosslinked effect (polymerization).In embodiments of the present invention, described can The supermolecule hydrogen bond action selectively contained, by the polymerization owner for being present in any appropriate ingredient in dynamic covalent polymer Formation hydrogen bond is constituted between appointing the hydrogen bond group of one or more in chain, side group, side chain, branch, end group.Wherein, the hydrogen Key group can also exist in small molecule and/or filler.In embodiments of the present invention, the hydrogen bond group preferably exists Synergistic effect is preferably played on the polymer chain containing B-O-Si keys, being conducive to dynamic covalent bond and hydrogen bond.

In embodiments of the present invention, can include one or more polymer in dynamic covalent polymer composition； It when there are cross-linked network, can be made of one or more cross-linked networks, noncrosslinking polymer can also be contained simultaneously Ingredient.When dynamic covalent polymer is made of two or more cross-linked networks, can be mutually blended by two or more Cross-linked network is constituted, and can also be made of two or more mutually interspersed cross-linked networks, can also be by two or more parts Mutually interspersed cross-linked network is constituted, but the present invention is not limited only to this；Wherein, two or more cross-linked networks can be identical, It can be different.When dynamic covalent polymer is simultaneously comprising crosslinking and when non-crosslinked ingredient, non-crosslinked ingredient can be with homogeneous blend/wear It is inserted in cross-linked network, can not also be evenly dispersed in cross-linked network；Between multiple non-crosslinked ingredients can with homogeneous blend or Person is incompatibly blended.

For the dynamic covalent polymer of the present invention, when dynamic covalent cross-linking reaches dynamic at least one cross-linked network When more than the gel point of state covalent cross-linking, it is ensured that even if only there are one in the case of cross-linked network, polymer can be There is cross-linked structure under specified conditions.

In the present invention, described " skeleton " refers to the chain length direction of polymer；It is described for cross-linked polymer " main chain " refers to the arbitrary segment being present in cross-linked network skeleton comprising main chain on unlimited three-dimensional network skeleton and Crosslinking link；For non-cross-linked polymer, " main chain " generally refers to the most chain of chain link unless stated otherwise.Wherein, institute " side chain " stated refers to that same main polymer chain skeleton is connected and is distributed in the chain structure of main chain backbone side；Wherein, described " branch "/" bifurcated chain " can be side chain chain structures that can also be other come out from arbitrary chain bifurcated.Wherein, described " side group " refers to that same polymer chain skeleton is connected and is distributed in the chemical group of chain backbone side.For " side chain ", " branch Chain " and " side group " can have multilevel hierarchy namely side chain/branch that can continue to carry side group and side chain/branch, and side chain/ Side chain/branch of chain can continue have side group and side chain/branch.Wherein, " end group " refers to the arbitrary chain of same polymer It is connected and is located at the chemical group of chain end.For hyperbranched and dendroid chain and its relevant branched chain structure, branch Main chain can be considered as, but in the present invention, the chain of outermost is considered as branch, other chains are considered as main chain.

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".

Dynamic and response based on the dynamic covalent bond and optional hydrogen bond, dynamic covalent polymer of the invention can To show diversified dynamic property and for the response performance of environmental stimuli, including but not limited to self-repairability, temperature Response, stress/strain response, especially dilatant performance.When the dynamic covalent polymer is non-crosslinking structure, system Viscous state will be remained as if even if dilatancy energy occurs under stress/strain effect, without generating elastic state, this phenomenon has Conducive to mechanical energy is lost by VISCOUS FLOW completely.When the dynamic covalent polymer is dynamic crosslinking structure, system When dilatant occurs, visco-elastic conversion or elasticity, which will occur, to be enhanced, and the viscous loss to external force can occur while reducing The destruction of external force.Two kinds of situations respectively have feature and advantage.The relevant self-repairability of dynamic, temperature-responsive are conducive to dynamic Covalent polymer carries out selfreparing, moulding and recycling etc., and the safety in utilization for increasing material, carries the service life for extending material Rise the machinability etc. of material.

In embodiments of the present invention, the inorganic boric acid estersil key (B-O-Si) is by inorganic compounds of boron and siliceous The silicon-containing compound of hydroxyl and/or silicone hydroxyl presoma reacts.

The inorganic compounds of boron refers to that the boron atom in compound does not contain boronation with carbon atom by what boron carbon key was connected Close object.

The inorganic compounds of boron is selected from (including but not limited to) boric acid, borate, borate, boric anhydride, halogenation boron.Boron Acid can be ortho-boric acid, metaboric acid, tetraboric acid.Borate includes the alkyl and allyl ylboronic acid for being hydrolyzed into boric acid in the presence of water The organic group borate of ester/tri-, such as trimethylborate, triethyl borate, triphenyl borate, three benzyl ester of boric acid, three hexamethylene of boric acid Ester, boric acid three (methyl silicane ester), three tert-butyl ester of boric acid, three-n-pentyl borates, three sec-butyl borates, DL- menthyls Borate, three (4- chlorphenyls) borates, 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids ester, three (2- methoxyl group second Base) borate, benzyl dihydro borate, diphenyl hydrogen borate ester, isopropanol pinacol borate, triethanolamine borate etc.. Suitable boric anhydride is B except including general formula₂O₃Outside typical boron oxide, further include but be not limited only to tri-alkoxy boroxin and Its derivative, for example, trimethoxy boroxin, three isopropoxy boroxins, 2,2 '-oxygen it is bis- [4,4,6- trimethyls -1,3, 2- dioxa boroxanes etc..Suitable borate includes but are not limited to five boric acid diammoniums, sodium borate decahydrate (borax), five Potassium borate, hypoboric acid magnesium, single line borate, three barium borates, zinc metaborate, tripotassium borate, ortho-boric acid molysite.Suitable halogenation boron Include but are not limited to boron trifluoride, boron chloride, Boron tribromide, triiodide boron, four chlorinations, two boron etc..Suitable inorganic boronation Close the partial hydrolysate that object further comprises aforementioned borate.Typically, it is B that inorganic compounds of boron, which is general formula,₂O₃[CAS is registered Number #1303-86-2] boron oxide or general formula be H₃BO₃The boric acid of [CAS registration numbers #10043-35-3].As an example, suitably The chemical structural formula of inorganic compounds of boron is as follows, however, the present invention is not limited thereto：

The silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma refers to that the end group of compound and/or side group contain There are silicone hydroxyl and/or silicone hydroxyl presoma group.In the present invention, at least partly silicon-containing compound must contain the connection Base L can generate the linker L by suitably reacting.It is preferred that the silicon-containing compound each contain silicone hydroxyl and/ Or silicon atom there are one being contained only in the end group and/or side group of silicone hydroxyl presoma group.Since linker L skeletons contain carbon original Son, especially linker containing carbon polymer can obtain the various dynamic covalent polymer skeleton of structure-rich, performance, especially The dynamic covalent polymer obtained with more strong mechanical performance, impressionability can be facilitated by being the presence of skeleton carbon, be also convenient for drawing Enter hydrogen bond action and obtains additional dynamic.In addition to the silicon-containing compound of the above-mentioned L containing linker, for generate B-O-Si keys its His silicon-containing compound can be selected from any appropriate small molecule or macromolecular silicon-containing compound, preferably polysiloxanes, can have Machine or inorganic polysiloxane compound, including silica.

Heretofore described silicone hydroxyl refers to a hydroxyl institute group being connected by silicon atom and with the silicon atom At structural motif (Si-OH), wherein silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with a carbon Atom is connected by silicon-carbon bonds, and at least one organic group is keyed to by the silicon-carbon on silicon atom) or nothing Machine silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, silicon A hydroxyl (- OH) in hydroxyl is a functional group.

Heretofore described silicone hydroxyl presoma, refer to one be connected by silicon atom and with the silicon atom can Hydrolysis obtains the structural motif (Si-Z) that the group of hydroxyl is formed, wherein Z is that hydrolyzable obtains the group of hydroxyl, optional From halogen, cyano, oxygen cyano, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketone Oximido, alkoxide group etc..Suitable silicone hydroxyl presoma citing is such as：Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃, Si- OB(OCH₃)₂, Si-NH₂, Si-N (CH₃)₂, Si-OCH₃, Si-COCH₃, Si-OCOCH₃, Si-CONH₂, Si-O-N=C (CH₃)₂, Si-ONa.In the present invention, the group (- Z) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is a functional group.

In order to illustrate the silicon-containing compound of the heretofore described L containing linker and its containing for the producible L containing linker Silicon compound can be exemplified below, but the present invention is not limited only to this,

Wherein m, n, the quantity that x, y, z is repetitive unit, can be fixed value or average value.

In the present invention, any appropriate inorganic compounds of boron may be used and contain silicone hydroxyl and/or silicone hydroxyl presoma Compound combination generate Inorganic Boron acid estersil key, it is preferred to use inorganic boric acid and the macromolecular compound containing silicone hydroxyl, nothing Machine boric acid and macromolecular compound, the inorganic borate (salt) of siliceous hydroxyl groups precursors come with the macromolecular compound containing silicone hydroxyl Form inorganic boric acid estersil key, more preferably using inorganic boric acid with containing silicone hydroxyl macromolecular compound, inorganic borate with contain The macromolecular compound of silicone hydroxyl forms inorganic boric acid estersil key, more preferably using inorganic borate and big point containing silicone hydroxyl Sub- compound forms inorganic boric acid estersil key.

In embodiments of the present invention, the Inorganic Boron oxygen boron key may be used any appropriate mode and generate, preferably It is generated by way of the dehydration of inorganic boric acid, inorganic boric acid and inorganic boric acid organic ester dealcoholysis.

In embodiments of the present invention, can by generate inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key come The dynamic covalent polymer is generated, can also first be prepared containing the inorganic boric acid estersil key and optional boron oxygen boron key Compound again polymerized/cross-linked to generate the dynamic covalent polymer.In the present invention, the polyvalency based on Si atoms, The Si atoms that L containing linker participates in being formed B-O-Si with one on the silicon-containing compound of other linkers can at most form three B-O-Si shares a Si atom.And since boron atom is trivalent structure, once material composition has suitable reactivity Group, polymerization process generates the inorganic boric acid estersil and Inorganic Boron oxygen boron key can be easy to cause and form bifurcated and can be into And it is crosslinked.

In embodiments of the present invention, for optional supermolecule hydrogen bond, the number of teeth does not limit.The number of teeth is served as reasons The hydrogen bond donor (D, that is, hydrogen atom) and hydrogen bond receptor (A, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group The hydrogen bond quantity of composition, each D-A are combined as a tooth and (are shown below, list a tooth, two teeth and three tooth hydrogen bond groups respectively Hydrogen bond bonding situation).

If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action with regard to weak, can play raising dynamic altogether The effect of valence mechanical properties of polymer (modulus and intensity).If the number of teeth of hydrogen bond is few, intensity is low, the dynamic of hydrogen bond action It is just strong, dynamic property can be provided together with dynamic covalently inorganic boric acid estersil key and Inorganic Boron oxygen boron key, such as self-repairability is inhaled Energy characteristic etc..In embodiments of the present invention, the preferably more than hydrogen bond action of four teeth, more preferably passes through side group and/or side Hydrogen bond group on chain participates in forming the hydrogen bond action no more than four teeth.

In embodiments of the present invention, the hydrogen bond group can be have simultaneously in a hydrogen bond group hydrogen bond receptor with Hydrogen-bond donor；Can also be that part hydrogen bond group contains hydrogen-bond donor, other part hydrogen bond group contains hydrogen bond receptor；It is preferred that same Shi Hanyou receptors and donor.

The hydrogen bond receptor of heretofore described hydrogen bond group can be any appropriate electronegative atom such as O, N, S, F, excellent Choosing contains at least one of structure shown in the following general formula (1),

Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Wherein,It indicates It is linked or the connection of any other suitable group (including hydrogen atom) with polymer chain, crosslinking.Wherein, R be selected from hydrogen atom, Replace atom, substituent group.

When as substituent group, the carbon atom number of R is not particularly limited, preferably carbon atom number be 1~20, more preferably 1~ 10。

When as substituent group, the structure of R is not particularly limited, including but not limited to linear chain structure, the branch link containing side group Structure or cyclic structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, excellent Select aliphatic ring.

When as substituent group, R can contain hetero atom, can not also contain hetero atom.

R can be selected from hydrogen atom, halogen atom, C_1-20Alkyl, C_1-20Miscellaneous alkyl, substituted C_1-20Alkyl or substituted miscellaneous hydrocarbon Base.Wherein, the substitution atom in R or substituent group are not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing heteroatomic It is any in substituent group.

R is more preferably hydrogen atom, halogen atom, C_1-20Alkyl, C_1-20Alkenyl, aryl, aryl, C_1-20It is fat miscellaneous alkyl, miscellaneous Aryl, heteroaryl alkyl, C_1-20Alkoxyacyl, aryloxy acyl group, C_1-20It is any in alkyl sulfenyl acyl group, artyl sulfo acyl group The substituted form of kind atom or group or any group.

Specifically, R can be selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, ethyl, n-propyl, different Propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, Pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, acrylic, vinyl, benzene Base, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto Carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzylaminocarbonyl, methoxyl group thiocarbonyl, second Oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, ethylmercapto group thiocarbonyl, benzene sulphur Base thiocarbonyl, benzylthio thiocarbonyl, ethylamino thiocarbonyl, benzyl aminothiocarbonyl, substituted C_1-20Alkyl, substitution C_1-20Alkenyl, substituted aryl, substituted aryl, substituted C_1-20Fat miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl hydrocarbon Base, substituted C_1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C_1-20Alkyl sulfenyl carbonyl, substituted aryl sulphur The C of base carbonyl substitution_1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C_1-20Alkyl alkylthio carbonyl Any atom or group in base, substituted artyl sulfo thiocarbonyl etc..Wherein, when the structure being related to has isomerism Can be any of which isomers, such as alkyl, without specially appointed feelings in the case of not specifying when body Under condition, refers to and lose the alkyl that the hydrogen atom of any position is formed, specifically if butyl includes but not limited to normal-butyl, tertiary butyl； Octyl includes but not limited to n-octyl, 2- ethylhexyls.Wherein, atom or substituent group is replaced to be selected from halogen atom, alkyl substitution Base, containing any in heteroatomic substituent group.

The hydrogen bond donor of heretofore described hydrogen bond group can be the donor groups of any appropriate hydrogen atoms, preferably Containing at least one of structure shown in the following general formula (2),

Wherein,Indicate with polymer chain, be crosslinked and link or the company of any other suitable group (including hydrogen atom) It connects.

Structure shown in general formula (1) and (2) can be side group, end group, chain structure etc., can also form cyclic structure.Its In, the cyclic structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure Deng.

In embodiments of the present invention, the hydrogen bond group preferably contains structure shown in general formula (1) and (2) simultaneously.

In embodiments of the present invention, at least one of further preferably following constituent of the hydrogen bond group：

Wherein,Indicate with polymer chain, be crosslinked and link or the company of any other suitable group (including hydrogen atom) It connects.In embodiments of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, thiocarbamate Base, silicon are for carbamate groups or the derivative etc. of the above group.

Skeleton hydrogen bond group citing such as (but the present invention is not limited only to this) on suitable chain backbone：

Suitable side group hydrogen bond group and end group 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.

In the present invention, one or more kinds of hydrogen bond groups can be contained in same compound/polymer, it is same Can also contain in one or more kinds of hydrogen bond groups namely dynamic covalent polymer in a cross-linked network can contain one The combination of kind or a variety of hydrogen bond groups.The hydrogen bond group can the main chain of linker L, side group, side chain, branch any one In place or many places, can also the main chain of other linkers, side group, side chain, branch any one or many places on.The hydrogen Key group can be formed by any appropriate chemical reaction, such as：Pass through carboxyl, acyl halide group, anhydride group, ester group, acyl It reacts to be formed between amido, isocyanate groups and amino；By between isocyanate groups and hydroxyl, sulfydryl, carboxyl Reaction is formed；It to be formed by reacting between succinimide ester groups and amino, hydroxyl, sulfydryl.

In the present invention, there is no limit for the content of hydrogen bond group and its hydrogen bond action.The supermolecule hydrogen bond action can be with It is generated during being the component of polymer formation in dynamic covalent polymer；Can also be that supermolecule hydrogen bond action is generated in advance The component of polymer in dynamic covalent polymer is re-formed afterwards；It can also be generated during dynamic covalent polymer subsequent forming Supermolecule hydrogen bond action, but the present invention is not limited only to this.

In the present invention, there can also be other diversified embodiments, in any one embodiment optionally Containing the Inorganic Boron oxygen boron key and/or hydrogen bond action, those skilled in the art can be with logic according to the present invention and arteries and veins Network is rationally and effectively realized.

The present invention also provides a kind of methods of energy-absorbing, which is characterized in that provides a kind of dynamic covalent polymer and is made with it Energy-absorbing is carried out for energy-absorbing material, wherein containing B-O-Si dynamic covalent bonds, wherein any one B in the dynamic covalent polymer Atom is connect with three-O-, and wherein former from the different Si in at least two B-O-Si dynamic covalent bonds based on different B atoms Contain the carbon on dynamic covalent polymer chain backbone containing linker L, the linker L in the linker that son is connected Atom.

In the present invention, the raw material components of dynamic covalent polymer are used to prepare, the inorganic compounds of boron of the foregoing description is removed Further include the other polymers that can be added/use, auxiliary agent, filler except silicon-containing compound, these can additive/can be used Object collectively constitutes the dynamic by the form of blending and the reaction product of inorganic compounds of boron and silicon-containing compound and covalently gathers Close object composition.

In embodiments of the present invention, the form of the dynamic covalent polymer or its composition can be solution, breast Liquid, cream, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, Ionic liquid swell gel), foam etc., wherein the small-molecular-weight component content contained in ordinary solid and foam is not generally high In 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Wherein, dynamic aggregation object is commonly solid The shape and volume of body are relatively more fixed, and intensity is high, and density is big, are suitable for the anti-explosion wall or apparatus housings of high intensity；Elasticity Body has the general properties of ordinary solid, but elasticity is more preferable, pliability higher, is more suitable for as the energy-absorbings material such as damping/damping Material；Dynamic aggregation object gel soft texture, there is preferable energy absorption capacity and elasticity, is suitable for preparing the energy-absorbing material of high-damping；It is dynamic For state polymer foams when having the advantages that the general foamed plastics such as density is low, light, specific strength is high, soft foam material is also With good elasticity and energy absorption capacity.

In embodiments of the present invention, dynamic covalent polymer gel is preferably by sweller (including water, You Jirong One of agent, oligomer, plasticizer, ionic liquid or combinations thereof) in carry out dynamic crosslinking acquisition, can also be covalently poly- in dynamic Closing after the completion of prepared by object recycles sweller to carry out swelling acquisition.Certainly, the present invention is not limited only to this, and those skilled in the art can With logic according to the present invention and train of thought, rationally and effectively realize.

In the preparation process of dynamic covalent polymer expanded material, mainly using mechanical foaming method, physical blowing method, change Three kinds of methods of foaming are learned to foam to dynamic covalent polymer.

Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic covalent polymer big Amount air or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through Physically or chemically variation is allowed to be gelled, cures and become foamed material.To shorten, molding cycle can be passed through air and addition emulsifies Agent or surfactant.

Wherein, the physical blowing method is using physical principle in the preparation process of dynamic covalent polymer come real The foaming of existing polymer, generally comprises following four method：(1) inert gas blown method, i.e., inertia under pressurized condition Gas is pressed into molten polymer or pasty material, and then decompression heating, makes the gas expansion of dissolving and foam；(2) using low Boiling-point liquids evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, make liquid Body dissolves in polymer beads, then heats and softens polymer, and liquid also gasifies therewith evaporation and foamed；(3) leaching, i.e., It is immersed in polymer with liquid medium and dissolves the solid matter added in advance, make to occur a large amount of holes in polymer and be in hair Blister, such as by solable matter salt, starch elder generation and mixed with polymers, water is placed on after being shaped to product, then by product In handle repeatedly, solable matter is dissolved out to get to open-celled foam product；(4) hollow microsphere method is added in the plastic Become obturator-type foamed plastics through solidification after hollow microsphere；Wherein, preferably by dissolving in inert gas and low in the polymer The method of boiling-point liquids foams.Using physical blowing method, have operation Poisoning smaller, foaming raw material cost is relatively low, hair The advantages that infusion noresidue body.Further, it is also possible to be prepared using freeze-drying.

Wherein, the chemical blowing process is generated along with chemical reaction in dynamic covalent polymer foaming process Gas and the method to foam, generally comprise following two methods：(1) thermal decomposable foaming agent foaming utilizes chemistry hair The gas decomposed to give off after infusion heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, i.e., it is sharp With the chemical reaction occurred between two or more components in foaming system, inert gas (such as carbon dioxide or nitrogen) is generated Polymer is caused to expand and foam.Polymerisation and foamable reaction balance carry out in order to control in foaming process, to ensure that product has A small amount of catalyst and foam stabiliser (or surfactant) is generally added in preferable quality.Wherein, preferably by polymer The method of middle addition chemical foaming agent foams.

In the preparation process of dynamic covalent polymer, it is preferred to use moulded from foam is molded, is injection-expansion molded and crowded Go out three kinds of methods of foaming to be molded dynamic covalent polymer 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 dynamic covalent polymer, those skilled in the art can prepare situation and mesh according to practical Mark polymer performance select suitable foaming method and foamed material forming method to dynamic covalent polymer foamed material into It is prepared by row.

In embodiments of the present invention, the structure of dynamic covalent polymer foamed material is related to open-celled structure, closed pore knot Structure, three kinds of half-open semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional are all Can be that 0.01-3mm is differed by gas or liquid, abscess diameter.Hole-closing structure has individual blisters structure, inner cell and bubble There is wall film to separate between hole, the overwhelming majority is not interconnected, and abscess diameter is that 0.01-3mm is differed.The existing phase of contained abscess It is intercommunicated and to have mutual disconnected structure then be half open-celled structure.It, also can be by machinery for having formed the foaming structure of closed pore Pressure or chemical method become open-celled structure, and those skilled in the art can select according to actual needs.

In embodiments of the present invention, dynamic covalent polymer foamed material is according to its softness, can be divided into it is soft, Hard and semi-rigid three classes：(1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be 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 covalent polymer foamed material can be divided into again according to its density low ratio foamed, Middle foaming and high-foaming.The foamed material of low ratio foamed, density are more than 0.4g/cm³, expansion ratio is less than 1.5；The bubble of middle foaming Foam material, density are 0.1~0.4g/cm³, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/cm³, expansion ratio is more than 9.

In embodiments of the present invention, the described other polymers added/used, auxiliary agent, filler can be arbitrary Suitable material.

Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Other polymerizations that can be added/use Object can be selected from natural polymer, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to the polymer that is added Character and possessed molecular weight do not limit, can be oligomer or high polymer, root according to the difference of molecular weight Can be homopolymer or copolymer according to the difference of polymeric species, it in the specific use process should be according to the performance of target material And actual fabrication process needs and selected.

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

When the other polymers are selected from synthetic resin, it can be selected from following any or appoint several synthetic resin： Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), makrolon, Dimethyl silicone polymer, polyethylene, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane Copolymer, polyimides, polymethyl acrylate, polymethyl methacrylate, polymethacrylonitrile, polyphenylene oxide, polypropylene, polyphenyl Thioether, polyphenylsulfone, polystyrene, high impact polystyrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, Ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, AAS acrylonitrile acryloid styrene, acrylic nitrile-butadiene Diene-styrene copolymer, vinyl chloride vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, urea Urea formaldehyde, unsaturated polyester (UP) etc..

When the other polymers are selected from synthetic rubber, it can be selected from following any or appoint several synthetic rubber： Isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorubber, Lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc..

When the other polymers are selected from synthetic fibers, it can be selected from following any or appoint several synthetic fibers： Viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane fiber, polypropylene Nitrile fiber, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..

In the preparation process of polymer material, the preferred natural rubber of the other polymers, polyethylene, polypropylene, Vinyl-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polymethyl methacrylate, ring Oxygen resin, phenolic resin, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, the third rubber of second Glue, silicon rubber, polyurethane rubber, thermoplastic elastomer (TPE).

The auxiliary agent for adding/using, can improve material preparation process, improve product quality and yield, drop Low product cost assigns product certain distinctive application performance.The auxiliary agent is selected from following any or appoints and several help Agent：Additive synthesis, including catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer；Improved force Learn the auxiliary agent of performance, including chain extender, toughener, coupling agent；Improve the auxiliary agent of processing performance, including lubricant, releasing agent；It is soft The auxiliary agent of softening and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change the auxiliary agent of surface property, including antistatic Agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；Fire retardantization is helped with suppression cigarette Agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent.

Catalyst in the auxiliary agent can reduce reaction activity to accelerate to react by changing reaction path The reaction rate of object during the reaction.In embodiments of the present invention, the catalyst includes but are not limited to：(1) Polyurethane catalyst for synthesizing：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (diformazan ammonia Base propyl) diisopropanolamine (DIPA), N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- bis- Methyl cyclohexylamine, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- bis- Methylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls caproic acid, N, N- diformazans Base benzylamine, N, N- dimethyl cetylamines etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, two pungent Base tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, acetic acid benzene Mercury, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc..(2) polyolefin catalyst for synthesizing：Such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, four chlorinations Titanium, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, three oxidations Two antimony, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc..(3) CuAAC reacts Concerted catalysis is shared by monovalence copper compound and amine ligand.Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr(PPh₃)₃ Deng；It can also be by elemental copper and cupric compound (such as CuSO₄、Cu(OAc)₂) in-situ preparation during the reaction；Wherein, Cu (I) the preferred CuBr (PPh of salt preferred CuBr and CuI, Cu (I) complex compound₃)₃.Amine ligand can be selected from three [(1- benzyls -1H-1,2,3- Triazole-4-yl) methyl] amine (TBTA), three [(1- tertiary butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzene And imidazolmethyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；Wherein, amine ligand preferred TBTA and TTTA.(4) Thiol-ene catalysts：Photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyls phenylacetone, 2,2- dimethoxies Base -2- phenyl acetophenones etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethylamino pyrroles Pyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01-2wt%.

Initiator in the auxiliary agent can cause monomer molecule to activate in polymerization process and generate free Base improves reaction rate, and reaction is promoted to carry out, and includes but are not limited to following any or appoints several initiators：Organic peroxy Compound, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, two hexamethylene of dicetyl peroxydicarbonate Bis- (4- tert-butylcyclohexyls) esters of ester, dicetyl peroxydicarbonate, tert butyl peroxy benzoate, tert-butyl hydroperoxide pivalic acid Ester, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, as azodiisobutyronitrile (AIBN), azo two are different Heptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred lauroyl peroxide of initiator, benzoyl peroxide Formyl, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1-1wt%.

Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, ensure that material can be smooth Ground carries out preparing processing and extends its service life, includes but are not limited to following any or appoints several antioxidant：Hindered phenol Class, 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-butylphenols)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert butyl benzene Phenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization Isocyanates Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as the N, (β-naphthalene of N '-two Base) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thio-2 acid Dilauryl, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, three nonyl of phosphorous acid Phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Used Antioxidant dosage is not particularly limited, generally 0.01-1wt%.

Light stabilizer in the auxiliary agent can prevent polymer samples from light aging occurs, extend its service life, It includes but are not limited to following any or appoints several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous Sour calcium；Ultra-violet absorber, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyls Base -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzotriazole, (the 2- hydroxyls of 2,4,6- tri- Base -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls；Pioneer's type is ultraviolet Light absorbers, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3,5- bis- tertiary fourths Base -4- benzylphosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer, such as the last of the ten Heavenly stems two Bis- (2,2,6,6- tetramethyl piperidines) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidines) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamates, N, N '-second, n-butyl dithiocarbamate nickel etc.；Wherein, Bis- (2,2,6,6- tetramethyl piperidines) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light stabilizer used is used Amount is not particularly limited, generally 0.01-0.5wt%.

Heat stabilizer in the auxiliary agent enables to polymer samples during processing or use not due to heated Chemical change occurs, or delays these variations to achieve the purpose that prolong the service life comprising but it is not limited only to following A kind of or several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, stearic acid Lead, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides 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；It is sub- Phosphoric acid ester, such as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphorous acid Ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Wherein, heat stabilizer is preferred Barium stearate, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not have It is particularly limited to, generally 0.1-0.5wt%.

Chain extender in the auxiliary agent can be such that strand expands with the reaction-ity group reaction on reactant molecule chain Exhibition, molecular weight increase comprising but be not limited only to following any or appoint several chain extenders：Polyalcohols chain extender, such as second two Alcohol, propylene glycol, diglycol, glycerine, trimethylolpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, to benzene Diphenol dihydroxyethyl ether (HQEE), resorcinol double hydroxyethyl ether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, Such as diaminotoluene, diamino dimethylbenzene, tetramethyl xylylen diamines, tetraethyl diphenyl methylene diamines, tetra isopropyl Hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminomethyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '- Diphenylmethanediamiand (MOCA), 3,5- dimethythiotoluene diamines (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1, 3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcamines chain extender, such as triethanolamine, triisopropanolamine, N, the bis- (2- of N '- Hydroxypropyl) aniline.Chain extender dosage used is not particularly limited, generally 1-20wt%.

Toughener in the auxiliary agent can reduce polymer samples brittleness, increase toughness, and it is strong to improve material carrying Degree comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-butadiene-styrene is copolymerized Resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylonitrile-butadiene-benzene second Alkene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-butadiene-benzene Ethylene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), benzene second Alkene-butadiene-styrene block copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS), Chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.

Coupling agent in the auxiliary agent can improve the interface characteristics of polymer samples and inorganic filler or reinforcing material Can, the viscosity of material melt is reduced in plastic processes, improves the dispersion degree of filler to improve processing performance, and then make system Product obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any or appoint several couplings Agent：Chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.；Wherein, The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.

Lubricant in the auxiliary agent can improve the lubricity of polymer samples, 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, hydroxy stearic acid；Fat Esters of gallic acid, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type is such as hard Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamides；Fatty alcohol and polynary Alcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate, Zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used Agent dosage is not particularly limited, generally 0.5-1wt%.

Releasing agent in the auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean comprising but It is not limited only to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber etc.；Wherein, The preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5-2wt%.

Plasticizer in the auxiliary agent can increase the plasticity of polymer samples so that the hardness of polymer, mould Amount, softening temperature and brittle temperature decline, and elongation, flexibility and flexibility improve comprising but be not limited only to following any Kind appoints several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, phthalic acid two Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl Bis- (13) esters of ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthaldehyde Sour two (2- ethyls) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester, 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, epoxy fat 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；Binary Alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat acid esters； Polyesters, as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester, phenyl alkylsulfonate, trimellitate, Citrate and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), two fourth of phthalic acid Ester (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5-20wt%.

Foaming agent in the auxiliary agent, can so that polymer samples foam pore-forming, to obtain light, heat-insulated, sound insulation, Flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Physical blowing agent, such as third Alkane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether, chlorine Methane, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, Ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-dinitroso is to benzene two Formamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, azo two are different Butyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide,-two sulphur of biphenyl -4,4 ' Acyl azide；Foamed promoter, as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, Lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, stearyl chloride, benzene diformazan Acyl chlorides, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, Thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, foaming agent is preferred Sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitros, N, N '- Dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used It is not particularly limited, generally 0.1-30wt%.

Dynamic regulation agent in the auxiliary agent can be promoted and adjust dynamic aggregation object dynamic, to be optimized Expected performance, be usually that either free carboxyl group or can provide or receive the compound of electronics pair with free hydroxyl, Include but are not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc..Dynamic tune used Section agent dosage is not particularly limited, generally 0.1-10wt%.

The deleterious charge assembled in polymer samples can be guided or eliminated, makes it by the antistatic agent in the auxiliary agent Not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several antistatic agents：The moon from Subtype 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, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, dodecane Base trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second Inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, bis- polyoxyethylene of N- lauryls-N, N- Alkenyl-N- ethylphosphonic acids sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fat Sour ethylene oxide adduct, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride；It is high Molecule-type antistatic agent, such as the ethylene oxide propylene oxide addition product, polyene propionamide N- quaternary ammonium salts substituent, poly- 4- of ethylenediamine Vinyl -1- acetone yl pyridines phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, ten Eight alkyl dimethyl ethoxy quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).It is used Antistatic agent dosage be not particularly limited, generally 0.3-3wt%.

Emulsifier in the auxiliary agent can improve in the mixed with polymers liquid comprising auxiliary agent between various composition phases Surface tension is allowed to form uniform and stable dispersion or emulsion, is preferred for carrying out emulsion polymerization/crosslinking, packet It includes but is not limited only to following any or appoints several emulsifiers：Anionic, such as higher fatty acid salt, alkylsulfonate, alkyl Benzene sulfonate, Negel, 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, alkane Yl pyridines salt；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, such as poly alkyl alcohol Ethylene oxide ether, alkyl phenol polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, glycerin fatty Acid esters, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc.； Wherein, the preferred neopelex of emulsifier, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM).Emulsifier used is not particularly limited, generally 1-5wt%.

Dispersant in the auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into tiny particle And be suspended in liquid, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, while can also prevent particle Sedimentation and cohesion, form and stabilize suspension comprising but be not limited only to following any or appoint several dispersants：Anionic, Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as aliphatic alcohol polyethenoxy Ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Wherein, dispersant preferably 12 Sodium alkyl benzene sulfonate, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.Dispersant dosage used does not have It is particularly limited to, generally 0.3-0.8wt%.

Colorant in the auxiliary agent can make polymeric articles show required color, increase surface color and polish, It includes but are not limited to following any or appoints several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium Red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang The bright red R of red HF3C, the plastics and 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 rose Rare essence, Oil Yellow etc.；Wherein, the selection of colorant need not be particularly limited to depending on color sample demand.Coloring used Agent dosage is not particularly limited, generally 0.3-0.8wt%.

Fluorescent whitening agent in the auxiliary agent can make contaminated substance obtain the sparkling effect of similar fluorite, It includes but are not limited to following any or appoints several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline type, benzo Oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent CBS), bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene) Dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.

Delustering agent in the auxiliary agent when incident light being enabled to reach polymer surfaces, occurs diffusing reflection, generates low The matt and delustring appearance of gloss comprising but be not limited only to following any or appoint several delustering agents：Settle barium sulfate, dioxy SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred silica of delustering agent.Used disappears Photo etching dosage is not particularly limited, generally 2-5wt%.

Fire retardant in the auxiliary agent can increase the flame resistance of material comprising but be not limited only to following any Or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol Ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organohalogen compounds are such as high Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethanes, deca-BDE, penta decane of perchloro- ring；Inorganic combustion inhibitor, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as the anti-butylene of chlorendic anhydride, bis- (2,3- dibromopropyls) two Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.

Nucleating agent in the auxiliary agent can be accelerated crystalline rate, increase knot by the crystallization behavior of change polymer Brilliant density and promote fine grain size, reach and shorten material molding cycle, improves the product transparency, lustrous surface, tension The purpose of the physical mechanical properties such as intensity, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but be not limited only to Under it is any or appoint several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, silica, two Benzal D-sorbite and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, the preferred silica of nucleating agent, two benzals D-sorbite (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.

Rheological agent in the auxiliary agent can ensure that polymer has good brushability and appropriate during film Coating thickness, the sedimentation of solid particle, can improve its redispersibility comprising but be not limited only to following when preventing storage A kind of or several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, lithium chloride, sulfuric acid Sodium, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, aluminium alkoxide, Titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanate derivates, acrylic acid Lotion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferred organobentonite of rheological agent, polyethylene wax, hydrophobic Modified alkaline swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, and one As be 0.1-1wt%.

Thickener in the auxiliary agent can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, from And meet various demands such as its stability and application performance during production, storage and use comprising but not It is only limitted to following any or appoints several thickeners：Lower-molecular substance, such as fatty acid salt, alkyldimethylamine oxide, aliphatic acid Single ethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut palm Sub- amido propyl betaine, titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, fine particle silica, colloid Aluminium, animal protein, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide Amine, polyvinyl pyrrolidone, polyethers etc.；Wherein, the preferred hydroxyl coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid are total Polymers.Thickener dosage used is not particularly limited, generally 0.1-1.5wt%.

Levelling agent in the auxiliary agent can ensure that the flat smooth of polymer coating film is uniform, improve film coated surface matter Amount improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Dimethyl silicone polymer, poly- methyl Phenyl siloxane, polyacrylate, organic siliconresin etc.；Wherein, the preferred dimethyl silicone polymer of levelling agent, polyacrylic acid Ester.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.

In the preparation process of dynamic covalent polymer, the auxiliary agent preferred catalyst, initiator, antioxidant, light are steady Determine agent, heat stabilizer, chain extender, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.

The filler primarily serves following effect in dynamic covalent polymer：1. reducing the contraction of moulded products Rate improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting polymer Viscosity；3. meeting different performance requirement, such as improves polymer material impact strength and compressive strength, hardness, rigidity and modulus, carries High-wearing feature improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. it is steady to assign light Qualitative and chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.

The filler, selected from following any or several fillers：Inorganic non-metallic filler, organic is filled out at metal packing Material.

The inorganic non-metallic filler includes but are not limited to following any or appoints several：Calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, 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, expanded perlite Powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass microballoon, foam microspheres, glass powder, cement, glass Fiber, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, crystalline substance Palpus is equal.

The metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, gold etc. and its Powder, nano particle and the fiber of alloy.

The organic filler includes but are not limited to following any or appoints several：Fur, natural rubber, asbestos, worm Glue, chitin, chitosan, protein, raw lacquer, shell powder, silk, artificial silk, phenolic aldehyde microballon, resin microbeads etc..

Wherein, the wire feeding 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, chitosan, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.

In the preparation process of dynamic covalent polymer, any appropriate material hybrid mode known in the art can be passed through The raw material centainly matched is prepared into dynamic covalent polymer by mixing, can be interval, semicontinuous or continuous processing shape The mixing of formula；Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic covalent polymer.It adopts Hybrid mode include but are not limited to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, Ball milling etc., wherein it is preferred that solution is stirred, melts and be stirred and melting extrusion.Energy in material mixed process provides Form includes but are not limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to be extruded into Type, injection moulding, compression molding, tape casting, calendering formation, cast molding.

In the preparation process of dynamic covalent polymer, other for adding/using that the foregoing description can also be added are poly- Object, auxiliary agent, filler are closed to collectively constitute dynamic covalent polymer compound system, but these add/be not necessarily all necessary using object 's.

The specific method for preparing dynamic covalent polymer 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.Can select during this to retain as needed solvent be made with solution, emulsion, paste, Polymer samples existing for the forms such as glue, or selection remove solvent and are made existing for the forms such as membranaceous, blocky, foam-like admittedly State polymer samples.When preparing dynamic covalent polymer in this approach, usually also need to that initiator is optionally added in a solvent Cause polymerization in a manner of polymerisation in solution and obtain dynamic covalent polymer, or dispersant and oil-soluble initiator preparation is added Cause polymerization in a manner of suspension polymerisation or slurry polymerization at suspension and obtain dynamic covalent polymer, or initiator is added It is configured to emulsion in a manner of emulsion polymerization with emulsifier and obtains dynamic covalent polymer to cause polymerization.Used solution Polymerization, suspension polymerisation, slurry polymerization and emulsion polymerization method, be well known to those skilled in the art and be 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, methanol, ethyl alcohol, chloroform, dichloromethane Alkane, 1,2- dichloroethanes, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, acetic acid isopropyl Ester, n-butyl acetate, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, Phosphate buffer solution, borate buffer solution etc.；It is preferred that deionized water, toluene, chloroform, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene Furans, dimethylformamide, phosphate buffer solution.In addition, solvent is also selected from oligomer, plasticizer, ionic liquid；Described Oligomer includes but are not limited to polyethylene glycol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid Body paraffin etc.；The plasticizer can be selected from classification described in the plasticizer in addible auxiliary agent, and which is not described herein again；It is described Ionic liquid be generally made of organic cation and inorganic anion, cation is usually that alkyl quaternary ammonium ion, alkyl quaternary are seen Imidazol ion, the alkyl-substituted pyridinium ions of N- etc. that ion, 1,3- dialkyl group replace；Anion is usually halide ion, four Fluoro boron acid ion, also has CF at hexafluorophosphoricacid acid ions₃SO₃ ^-、(CF3SO₂)₂N^-、C₃F₇COO^-、C₄F₉SO₃ ^-、CF₃COO^-、 (CF₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₂F₅SO₂)₂N^-、SbF₆ ^-、AsF₆ ^-Deng.Wherein, dynamic is prepared covalently using deionized water Polymer simultaneously selects when being retained, and can obtain hydrogel；Dynamic covalent polymer is prepared using organic solvent and is selected When being retained, organogel can be obtained；It, can when preparing dynamic covalent polymer using oligomer and selecting to be retained To obtain oligomer swell gel；When preparing dynamic covalent polymer using plasticizer and selecting to be retained, it can obtain Plasticizer swell gel；When preparing dynamic covalent polymer using ionic liquid and selecting to be retained, ion can be obtained Liquid swell gel.

In above-mentioned preparation method, the compound liquid concentration configured 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 dynamic covalent polymer is stirred using melting, it is typically that raw material is straight in the reactor It connects and is stirred reaction after being stirred or heating melting, such mode is generally gas, liquid or lower melting-point in raw material It is used in the case of solid.In general, the control of hybrid reaction temperature at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixes Mixing time control is closed 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, 0-48h is placed, polymer samples are obtained.Dynamic is prepared in this approach covalently When polymer, usually also needs to be optionally added into a small amount of initiator and polymerize to cause in a manner of melt polymerization or gas-phase polymerization To dynamic covalent polymer.The method of its used melt polymerization, gas-phase polymerization, is well known to those skilled in the art And widely used polymerization, it can be adjusted according to actual conditions, no longer be developed in details here.

It is mixed with the specific method of dynamic covalent polymer using melting extrusion, is typically to add the raw material into extruder In carry out extrusion blending reaction, extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be cut out after direct tape casting At suitable dimension, either obtained extrusion sample is carried out to utilize injection molding machine or moulding press to carry out sample preparation after being crushed.Injection molding temperature Degree 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 be by batten It is placed in suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0-48h, obtain final polymer-like Product.

In the preparation process of dynamic covalent polymer, selected inorganic compounds of boron and the siliconization containing silicone hydroxyl The molar equivalent ratio for closing object should be at range appropriate, carry out the molar equivalent of other reactive groups of polymerized/cross-linked reaction Than, preferably 0.1~10 range, more preferable 0.3~3 range, more preferable 0.8~1.2 range.In actual fabrication process In, those skilled in the art can be adjusted according to actual needs.

In the preparation process of dynamic covalent polymer, spy is not done to the dosage of dynamic covalent polymer each component raw material Other restriction, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

The dynamic covalent polymer performance is adjustable on a large scale, in military aerospace equipment, functional paint and coating, biology The fields such as medical material, the energy, building, bionical, intellectual material, all have broad application prospects.

By using dilatancy possessed by dynamic covalent polymer, it is explosion-proof etc. that well recovery, fuel oil can be applied to Aspect, it may also be used for prepare speed lockup's device of road and bridge.When vibrated, can dissipate polymer material a large amount of energy Amount plays damping, to effectively mitigate the vibrations of vibration body, can be applied to making damping shock absorber, for various The vibration isolation of motor vehicles, mechanical equipment, bridge, building；As energy-absorbing buffering material, it is applied to buffer packaging material Material, athletic protective article, the police protective materials of surge guard product and army etc., to reduce article or human body in external force Effect lower suffered vibrations and impact, include the shock wave etc. of explosion generation；As energy-absorbing material, can also carry out sound insulation, Eliminate the noise etc.；It can be also used for making antidetonation shear plate or pulsating stress carrying tool, or for making stress monitoring sensor. Using wherein dynamic covalent bond, the intensity of supermolecule hydrogen bond and dynamic sex differernce, can also be carried out as shape-memory material It uses；By dynamic reversibility possessed by dynamic covalent polymer and rate of stressing dependence, stress sensitive type is prepared Polymer material, a part can be applied to prepare the toy and body-building material of the magic effect with mobility and elasticity conversion Material.It is carried out using inorganic boric acid estersil key as key can be sacrificed in use, it under external force can be by absorbing a large amount of energy And polymer material is assigned with excellent toughness, it is hereby achieved that thin polymer film, fiber or plank that toughness is splendid, extensively It is general to be applied to the fields such as military affairs, space flight, movement, the energy, building.

Dynamic reversibility and suitable component selection and formula based on inorganic boric acid estersil key design, and can also design Prepare preparation, coating, film, sheet material, proximate matter, plank etc. with self-repair function.Such as, dynamic covalently polymerization is made full use of Self-repairability possessed by object can prepare the binder with self-repair function, be applied to the gluing of various types of materials, also may be used As bulletproof glass squeegee, or it is used to prepare with good plasticity and can recycle the polymer closure glue of reparation；Base In the dynamic reversibility of inorganic boric acid estersil key, it can design and prepare the scratch resistant coatings with self-repair function, to prolong The service life of long coating is realized and is protected to the long-effective corrosion of basis material；It is designed by suitable component selection and formula, it can To prepare polymer gasket or polymer plate with self-repair function, so as to the original of mimic biology bulk damage healing Reason so that material can carry out self-healing to internal or outer damage, eliminate hidden danger, extend the service life of material, Huge application potential is shown in the fields such as military project, space flight, electronics, bionical.

Dynamic covalent polymer 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

By oligomeric polymethyl hydrogen siloxane (PHMS, molecular weight 500) and acryloyl-oxy eicosyl trimethoxy silane Mixing controls the molal quantity and propylene of active hydrogen atom (hydrogen atom being directly connected with Si) in polymethyl hydrogen siloxane in reaction The ratio of pivaloyloxymethyl trimethoxy silane double bond molal quantity is about 1:1, addition reaction occurs using chloroplatinic acid as catalyst, Obtained side group contains the organopolysiloxane of trimethoxy silicon group.

Above-mentioned organopolysiloxane, hydroxy-end capped dimethyl silicone polymer (molecular weight 700) and trimethylborate are pressed According to Si-OCH₃The molar ratio 1 of group, Si-OH groups and B-OR groups:1:2 mixing, are warming up to 80 DEG C after mixing, to The deionized water of 4ml is added in 100g mixtures, then is added dropwise to a small amount of acetic acid, then 1.0g graphenes, 0.5g are added wherein Organobentonite carries out polymerisation under stirring, and a kind of dynamic aggregation containing inorganic boric acid estersil key is prepared Object.

Obtained polymer samples are in rubber-like, can be stretched on a large scale under slower rate of extension, and creep occurs；With Finger is restored slowly or can not be restored after gently pressing；If but Rapid stretching or percussion, demonstrate flexibility feature.Because of its conductivity Sensitive response can occur with pressure or pulling force, be suitable as force snesor.

Embodiment 2

By the Polymethyl methacrylate (molecular weight about 20000) and 2- t-butoxycarbonyl amino second sulphur of methoxy group Alcohol, 3- mercaptopropyl trimethoxysilanes according to double bond and the compound of two sulfydryls molar ratio 3:2:1 mixing, be added relative to The photoinitiator benzoin dimethylether (DMPA) of 2- t-butoxycarbonyl amino ethyl mercaptans 0.2wt% is placed on ultraviolet after stirring fully It is crosslinked ultraviolet radioactive 4h in instrument, obtains that a kind of organopolysiloxane containing side hydrogen bond group is prepared.

The above-mentioned organopolysiloxane containing side hydrogen bond group, 1,7- dichlorooctamethyltetrasiloxanes and 2,6- di-tert-fourths Base -4- tolyl dibutyl ortho-boric acid esters are according to Si-OCH₃The molar ratio 1 of group, Si-Cl groups and B-OR groups:1:2 is mixed Close, take 100g mixtures, be warming up to 80 DEG C after mixing, be added 4.2g microballoon foaming agents, 2g ammonium polyphosphate, 4ml go from Sub- water quickly stirs 30s after mixing, and continuation is stirred to react 4h in nitrogen atmosphere, and one kind is prepared and contains side hydrogen bond The flexible foamed silicone materials of group and boric acid estersil key.

Reactant is poured into suitable mold, is placed in 60 DEG C of vacuum drying ovens that the reaction was continued for 24 hours, is cooled to room later Temperature places 30min, and foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, clamp time 10- 15min, pressure 10MPa, sample can carry out the good self-repair function that extends and have in a certain range, can be used as certainly Prosthetic glass sandwich glue has durability.

Embodiment 3

Two (3- morpholines ethoxysilylpropyl) (Z)-but-2-enes, two acid esters and ethoxy ylboronic acid are according to molar ratio 1: 1 mixing, takes 100g mixtures, after being warming up to 80 DEG C, the deionized water of 10ml is added, polymerisation is carried out under stirring, A kind of dynamic aggregation object containing boric acid estersil key is prepared.

The product shows good dilatancy, has good energy-absorbing effect, is also used as with magic elasticity Toy.

Embodiment 4

By boric acid and acrylic dimethylchlorosilane according to molar ratio 1:3 mixing, using triethylamine as catalyst, at 80 DEG C The boric acid estersil compound 4 that end carries double bond is prepared in reaction 12h.

The propylene glycol mono allyl ether of ethyl isocyanate and equimolar equivalent is dissolved in dichloromethane, under triethylamine catalysis Obtain (allyloxy) ethyl carbamate.

Two mercaptan of 20g polyethers is added in three-necked flask, 6.8g above-mentioned ends carry the boric acid estersil compound 4 of double bond, Above-mentioned (allyloxy) the ethyl carbamates of 3.2g, then it is placed on ultraviolet radioactive 8h in UV crosslinking instrument, it obtains one kind and contains There is the dynamic aggregation object of side hydrogen bond group and boric acid estersil key.

The polymeric articles can slowly extend under the effect of extraneous tensile stress, obtain (the fracture of super extension effects Elongation is up to 3000%).In the present embodiment, it can rushed using polymer samples obtained as the squeegee of bulletproof glass It hits under force effect and plays the effect of dissipative stress.

Embodiment 5

The limonene oxide extracted from orange peel is issued with 100psi carbon dioxide in the catalytic action of beta-diimine zinc Raw polymerisation, obtains makrolon PLimC.

By above-mentioned makrolon PLimC and γ-mercapto hydroxypropyl methyl dimethoxysilane, N- [(2- mercaptoethyls) amino first Acyl] propionamide according to double bond group and sulfydryl ratio is 10:5:5 mixing, are added the AIBN of 0.3wt%, by click-reaction system Obtain the makrolon that side group contains hydrogen bond group and methoxy silane groups.

Weigh the makrolon and (the 2- methoxyl groups of 10g tri- that the above-mentioned side groups of 45g contain hydrogen bond group and methoxy silane groups Ethyl) borate, it is thoroughly mixed uniformly, after being warming up to 80 DEG C, the deionized water of 10ml is added, is added dropwise to a small amount of second Acid adds polymer foaming microballoon, the 0.2mg BHT antioxidant of 2.5g, is quickly stirred through professional equipment to bubble is generated, so It is injected into mold rapidly afterwards, cures 30min at room temperature, then cure 4h at 80 DEG C containing side hydrogen bond base to get to one kind The foamed material of group and boric acid estersil key.

This foamed material has good chemical resistance, can replace polymer material obtained as glassware Dai Pin, hard packing box, dalle are used, have toughness and durability, while have good self-repairability and Biodegradability.

Embodiment 6

By dimethylallylchlorosilane and two mercaptan of the 1,10- last of the ten Heavenly stems according to molar ratio 2:1 mixing, using AIBN as initiator, Triethylamine is catalyst, and the silicon-containing compound of dimethylallylchlorosilane sealing end is made by thiol-ene click-reactions.

By above-mentioned silicon-containing compound and boric acid according to molar ratio 1:2 are mixed, and are thoroughly mixed uniformly, take 100g mixed Object is closed, after being warming up to 80 DEG C, the deionized water of 4ml is added, polymerisation 8h is carried out under stirring, one kind is prepared and contains There is the dynamic aggregation object of boron oxygen boron key and boric acid estersil key.

The polymeric articles have good dilatancy, can be as the materials'use of speed lockup's device.

Embodiment 7

(1) by oligomeric polyvinyl alcohol (PVA) (molecular weight is about 500) and a certain amount of 3- isocyanate group propyl front three Oxysilane mix, using triethylamine as catalyst, react in methylene chloride, control reaction in PVA hydroxyls molal quantity with The ratio of isocyano molal quantity is about 1:1.2, it obtains a kind of side group and contains carbamate groups and trimethoxy silicon group Polyol oligomer.

Above-mentioned side group contain carbamate groups and trimethoxy silicon group polyol oligomer and boric acid according to Si- OCH₃The molar ratio 1 of group and B-OH groups:1 mixing, is warming up to 80 DEG C after mixing, then be added dropwise to 20% a small amount of acetic acid Solution carries out polymerisation 8h under stirring, and the epoxidized soybean oil and 3wt% carbon nanotubes of 80wt% is then added, stirs After mixing fully swelling for 24 hours, a kind of dynamic of the epoxy soybean oil swell containing side hydrogen bond group and boric acid estersil key is prepared Polymer organic gel.

In the present embodiment, which has not only embodied preferable mechanical property, and has and can review one's lessons by oneself The functional characteristics such as multiple, pH responses.Obtained organogel has excellent toughness.

Embodiment 8

By the PEG (molecular weight is about 25000) and 3.2g diphenyl hydrogen of four arms of the ends 20g with trimethoxy silicon group Borate mix, be warming up to 80 DEG C stir evenly after, the deionized water of 4ml is added, polymerisation is carried out under stirring, make It is standby to obtain a kind of dynamic aggregation object containing boric acid estersil key.

Above-mentioned dynamic aggregation object is further swollen with deionized water, dynamic aggregation object hydrogel can be obtained.It should The excellent self-repairability that dynamic aggregation object hydrogel has can be used as aqueous medical dressing.

Embodiment 9

Using allyl alcohol as initiator, stannous octoate is catalyst, causes 6-caprolactone ring-opening polymerisation and obtains alkene list sealing end Polycaprolactone, then it is obtained to the polycaprolactone of alkene bi-end-blocking with acroleic acid esterification, then by itself and γ-mercapto propyl trimethoxy silicon For alkane using AIBN as initiator, triethylamine is catalyst, and obtaining trimethoxy silane sealing end by thiol-ene click-reactions gathers oneself Lactone.

Above-mentioned silane trimethoxy silane terminated polycaprolactone and trimethylborate are according to Si-OCH₃Group and B-OR groups Molar ratio 1:1 mixing, takes 20g blends, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, and 1mL is added The nano clay of 200 mesh of triethylamine and 200mg, carries out polymerisation under stirring, and one kind is prepared and contains boric acid silicon The dynamic aggregation object of ester bond.

Polymer samples obtained can be stretched in a certain range.In addition, after sample surfaces are carried out small cut, It is placed in 50 DEG C of mold after applying certain pressure fitting 2h, cut disappears, and has good selfreparing effect.This polymer Product can be as the packaging material of scratch-proof function and degradability.

Embodiment 10

Using hydroxy-ethyl acrylate as monomer, hydroxyethyl acrylate (molecular weight is about 800) is made by free radical polymerization.

By above-mentioned oligomeric hydroxyethyl acrylate and 2- furfuryl groups isothiocyanates, 3- isocyanate group propyl trimethoxies Silane mixture (is 2 by hydroxyl and isocyanates molar ratio:1.1:1.1), using triethylamine as catalyst, in methylene chloride instead It answers, obtained side group contains the polyacrylate of thiocarbamate group and trimethoxy silane group.

Above-mentioned side group contain thiocarbamate group and trimethoxy silicon group polyacrylate and boric acid according to Si-OCH₃The molar ratio 1 of group and B-OH groups:1 mixing, is warming up to 80 DEG C after mixing, and 2g white carbons, 3g titanium whites is added Powder, 1.5g cellulose crystallites, 2.2g di-iron trioxides carry out polymerisation 8h under stirring, obtain one kind and containing side hydrogen The dynamic aggregation object of key group and boric acid estersil key.

The polymeric articles can be used for preparing a kind of polymer gasket or polymer plate with self-repair function.

Embodiment 11

By styrene and styrene ethyl trimethoxy silane according to molar ratio 2:1 is mixed, using AIBN as initiator, The polystyrene being modified containing terminal siloxane is made using by free-radical polymerized.It is silicone-modified to weigh 15g above-mentioned ends Polystyrene and 3.2g trimethylborates be added in the beaker of dried and clean, pour into the toluene solvant of 120ml wherein, add After heat is dissolved to 60 DEG C by stirring, mixed liquor is placed in suitable mold in 60 DEG C of vacuum drying ovens later dry For 24 hours, hard block polymer solids are finally obtained.

The product its with higher case hardness and good mechanical strength, be put into mold and be heated to 180 DEG C, Compression molding 5min under 5MPa pressure is made into the dumbbell shape batten of 80.0 × 10.0 × 4.0mm sizes, utilizes tension test Machine carries out extension test, and rate of extension 10mm/min, it is 8.34 ± 2.18MPa to measure sample tensile strength, and stretch modulus is 19.45 ± 2.57MPa can be substituted with good chemical resistance using polymer material obtained as glassware Product, hard packing box are used.

Embodiment 12

(1) by 3- aminopropyltriethoxies dimethoxysilane and Adipoyl Chloride according to molar ratio 2:1 mixing, using triethylamine as Catalyst reacts in anhydrous methylene chloride, and disiloxane end-caps is prepared.

The above-mentioned disiloxane end-caps of 8.0g and 2.5g boric acid are weighed, 60 DEG C is heated to and is reacted by stirring 8h obtains a kind of dynamic aggregation object containing boric acid estersil key and boron oxygen boron key, as the 1st network polymer.

(2) by allyl hydroxyethyl ether and 5- chloromethyl -2- oxazolidones in molar ratio 1:1 is dissolved in toluene, with potassium carbonate For catalyst, tetrabutylammonium bromide is consisting of phase-transferring agent, obtains the olefinic monomer 12a containing oxazolidone group.

Under the conditions of anhydrous and oxygen-free, by allyl mercaptan and 2- thiophene isocyanates in molar ratio 1:1 is dissolved in dichloromethane, three Ethamine is catalyzed, and obtains the olefinic monomer 12b containing thio carbamate groups.

Olefinic monomer 12a olefinic monomers 12b in molar ratio 50:50 are sufficiently mixed, and 80 parts of epoxidized soybean oils are added, and stirring is filled After dividing mixing, swells in the 1st network polymer, add the AIBN of 5mol%, one kind being prepared by free radical polymerization The dynamic aggregation object organogel of epoxy soybean oil swell containing side hydrogen bond group and boric acid estersil key, boron oxygen boron key.

The dynamic aggregation object organogel of this epoxy soybean oil swell has soft elasticity, can be used for manufacturing a kind of energy-absorbing Material.

Embodiment 13

By the one end 25g be silicone hydroxyl sealing end polyethylene glycol (molecular weight about 5000), the both ends 2g be silicone hydroxyl sealing end gather Ethylene glycol (molecular weight about 2000) and the mixing of 2.2g trimethylborates, are warming up to 80 DEG C after mixing, 10mL deionizations are added The nano silicon dioxide of water and 100mg grain sizes 25nm, ultrasonic wave disperse 1h, and polymerisation 8h is carried out under stirring, is obtained A kind of non-crosslinked dynamic aggregation object containing boric acid estersil key and boron oxygen boron key.

The polymeric articles can be used as the additive of lubricating oil, the service life for improving lubricating oil.

Embodiment 14

Polybutadiene and thiopurine methyltransferase methyldiethoxysilane are mixed, it is 5 to keep the molar ratio of alkenyl and sulfydryl:1, with For DMPA as photoinitiator, ultraviolet light is light source, and the polybutadiene of side group silicone-containing group is made by click-reaction.It weighs The polybutadiene and 4.7g tri- (4- chlorphenyls) borate of the above-mentioned side group silicone-containing groups of 18g, are heated to 60 DEG C and pass through stirring After being dissolved, it is added a small amount of 20% acetic acid aqueous solution the reaction was continued 4h, it is poly- to obtain a kind of dynamic containing boric acid estersil key Close object.

The polymeric articles can be used for preparing with good plasticity and can recycle the polymer closure glue of reparation.

Embodiment 15

3- chloropropyls dimethyl methoxy silane and boric acid are mixed according to equimolar ratio, are heated to 60 DEG C and are carried out by stirring After dissolving, a small amount of water reaction 3h is added, obtains a kind of boronic acid compounds containing boric acid estersil key.

4,4'- is joined silicon benzene alcohol and the above-mentioned boronic acid compounds containing boric acid estersil key to mix according to equimolar ratio, takes 30g Mixture is heated to 80 DEG C, and the graphene oxide of 10mL deionized waters and 1.5g is then added, and the reaction was continued 8h obtains one kind Non-crosslinked dynamic aggregation object containing boric acid estersil key.

The polymeric articles can be used for preparing a kind of bonding agent with self-repair function.

Embodiment 16

By trimethylborate and dimethyl methyl oxygroup -3- butylene silane according to molar ratio 1:3 mixing, are heated to 60 DEG C and pass through After stirring is dissolved, it is added a small amount of water the reaction was continued 4h, obtains a kind of trivinyl compound containing boric acid estersil key.

The above-mentioned trivinyl compound containing boric acid estersil key and trimethylolpropane tris (2- mercaptoacetates) are pressed According to molar ratio 1:1 is mixed, and ultraviolet radioactive 8h in UV crosslinking instrument is placed on, and it is poly- to obtain a kind of dynamic containing boric acid estersil key Close object.

The polymeric articles can be used as sheet material or coating with selfreparing and recyclable function.

Embodiment 17

Using BPO as initiator, methyl vinyl diethoxysilane is subjected to graft reaction with low density polyethylene (LDPE) and is made A kind of silane grafted polyethylene.

Weigh 5g trimethylborates, 65g silane grafted polyethylenes (molecular weight is about 6000), 35g low density polyethylene (LDPE)s, 8g Decabromodiphenylethane, 2g antimony oxides, 1g polytetrafluoroethylene (PTFE) anti-dripping agent, 1.0g cumyl peroxides, 1g stearic acid, 0.2g antioxidant 1010s, 0.2g di-n-butyltin dilaurates, 0.5g dimethicones after mixing, are warming up to 150 DEG C, add 15MPa is pressed, 15min is molded, then print obtained is placed in 90 DEG C of water and reacts 2h, then takes out, is placed in mold, 4h is placed under the conditions of 120 DEG C of nitrogen protections to be dried, and obtains a kind of polyethylene-based material containing boric acid estersil key.

The polymeric articles can be molded again, embody recuperability.And there is excellent comprehensive performance, embody Good mechanical strength and impact resistance can be used as a kind of anti-ballistic materials use.

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

1. a kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B is former Son connect with three-O-, and wherein from the different Si atoms in at least two B-O-Si dynamic covalent bonds based on different B atoms Contain the carbon on dynamic covalent polymer main chain backbone containing linker L, the linker L in the linker being connected Atom.

2. a kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B is former Son connect with three-O-, and wherein from the different Si atoms in at least two B-O-Si dynamic covalent bonds based on different B atoms The linker being connected is linker L, and the linker L contains the original of the carbon on dynamic covalent polymer main chain backbone Son.

3. a kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B is former Son is connect with three-O-, and the arbitrary difference Si atoms in B-O-Si dynamic covalent bonds wherein different from least two are connected The linker connect is that linker L, the linker L contain the carbon atom on dynamic covalent polymer main chain backbone.

4. a kind of dynamic covalent polymer, which is characterized in that wherein contain B-O-Si dynamic covalent bonds, wherein any one B is former Son is connect with three-O-, and wherein from the arbitrary divalent that Si atoms are connected in arbitrarily different B-O-Si dynamic covalent bonds and The above linker of its divalent is linker L, and the linker L contains the original of the carbon on dynamic covalent polymer main chain backbone Son.

5. dynamic covalent polymer according to any one of claims 1 to 4, which is characterized in that wherein also contain B-O-B Key.

6. dynamic covalent polymer according to any one of claims 1 to 4, which is characterized in that it contains its group Also contain hydrogen bond action in.

7. dynamic covalent polymer according to any one of claims 1 to 4, which is characterized in that it contains its group At with following any character：Solution, lotion, cream, gel, ordinary solid, elastomer, foam.

8. dynamic covalent polymer according to any one of claims 1 to 4, which is characterized in that its formula group formed Point further include it is following any or appoint it is several can additive：Other polymers, auxiliary agent, filler；

Wherein, the other polymers are selected from following any or appoint several：Natural polymer, synthetic resin, conjunction At rubber, synthetic fibers；

Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, heat are steady Determine agent, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, breast Agent, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent；

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

9. dynamic covalent polymer according to any one of claims 1 to 4, which is characterized in that it is applied to following system Product：Damper, padded coaming, acoustic material, deadener, defense of resistance to impact material, athletic protective article, army and police protect system Product, self-repairability coating, self-repairability plank, self-repairability binder, bulletproof glass squeegee, toughness material, shape memory Material, sealing element, toy, force snesor.

10. a kind of method of energy-absorbing, which is characterized in that provide a kind of dynamic covalent polymer and the progress using it as energy-absorbing material Energy-absorbing, wherein containing B-O-Si dynamic covalent bonds, wherein any one B atom and three-O- in the dynamic covalent polymer Connection, and the company being wherein connected from the different Si atoms in at least two B-O-Si dynamic covalent bonds based on different B atoms It connects in base and contains the carbon atom on dynamic covalent polymer main chain backbone containing linker L, the linker L.