CN108341951A - A kind of dynamic aggregation object and its application with hybrid cross-linked structure - Google Patents

A kind of dynamic aggregation object and its application with hybrid cross-linked structure Download PDF

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CN108341951A
CN108341951A CN201710056069.XA CN201710056069A CN108341951A CN 108341951 A CN108341951 A CN 108341951A CN 201710056069 A CN201710056069 A CN 201710056069A CN 108341951 A CN108341951 A CN 108341951A
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hydrogen bond
linking
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CN108341951B (en
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不公告发明人
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Xiamen Tiance Material Technology Co ltd
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Weng Qiumei
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
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    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/02—Polythioethers; Polythioether-ethers

Abstract

The invention discloses a kind of dynamic aggregation objects with hybrid cross-linked structure, it includes have common covalent cross-linking while including the dynamic supermolecule hydrogen bond action that covalently inorganic boric acid estersil key and side hydrogen bond group participate in, wherein, common covalent cross-linking reaches its gel point or more.By dynamic, covalently inorganic boric acid estersil key is combined such dynamic aggregation object with supermolecule hydrogen bond, has good dynamic reversibility, and reflect the functional characteristics such as stimulating responsive, self-repairability；And common covalent cross-linking imparts polymer with certain strength and stability.In addition, the presence of inorganic boric acid estersil key and hydrogen bond, also enables polymer play good energy-absorbing effect, toughening and damping are carried out to material in specific structure.The dynamic aggregation object can be used for making damping, buffering material, defense of resistance to impact material, self-repair material, toughness material etc..

Description

A kind of dynamic aggregation object and its application with hybrid cross-linked structure
Technical field
The present invention relates to intelligent polymer fields, and in particular to one kind is by common covalent bond, dynamic covalent bond and supermolecule The dynamic aggregation object with hybrid cross-linked network and its application that hydrogen bond is constituted.
Background technology
Traditional three-dimensional net structure is generally formed by common covalent cross-linking, and common covalent bond is due to higher key Can, polymer is imparted with good stability and stress bearing capacity, therefore occupies larger ratio in the crosslinking of polymer Example.But when only with common covalent cross-linking, if crosslink density is relatively low, often cross-linking effect can not embody, especially It is that mechanical property is bad；And if crosslink density is higher, it is hard and crisp to often lead to cross-linked polymer；And general chemistry is handed over Connection lacks dynamic, is chemically crosslinked once being formed, crosslinking itself will be unable to change, and the performance of polymer material is immobilized.
Therefore, it is necessary to develop a kind of novel hybrid cross-linked dynamic aggregation object so that system can either have dimensionally stable Property, and have good mechanical property and excellent dynamic, to solve problems of the prior art.
Invention content
The present invention is directed to above-mentioned background, a kind of dynamic aggregation object with hybrid cross-linked network structure is provided, wherein extremely Include a covalent cross-linking network less, it is therein common covalently cross-linked to reach gel point or more；Simultaneously comprising the covalent nothing of dynamic The supermolecule hydrogen bond action that machine boric acid estersil key and side hydrogen bond group participate in.The dynamic aggregation object is with certain mechanics While intensity and good toughness, excellent dynamic reversibility is also shown, and reflects stimulating responsive, selfreparing The functional characteristics such as property, tack.
The present invention is achieved by following technical solution：
A kind of dynamic aggregation object with hybrid cross-linked structure wherein at least includes a covalent cross-linking network, therein The degree of cross linking of common covalent cross-linking reaches its gel point or more；Simultaneously comprising the covalent inorganic boric acid estersil key of dynamic and side hydrogen bond base The supermolecule hydrogen bond action that group participates in.
In an embodiment of the invention, the dynamic aggregation object is only there are one network, simultaneously comprising general in network Logical covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reaches its gel point or more, institute The dynamic covalent cross-linking stated is realized that the supermolecule hydrogen bond crosslinks include that the side hydrogen bond is made by inorganic boric acid estersil key With.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network includes Common covalent cross-linking and dynamic covalent cross-linking, wherein the common covalent cross-linking reaches its gel point or more, the dynamic Covalent cross-linking is realized by inorganic boric acid estersil key, does not contain the side hydrogen bond group in side group and side chain；In 2nd network not Containing covalently cross-linked, but polymer chain there are the side hydrogen bond group and participates in hydrogen bond crosslinks.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network includes Common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein the common covalent cross-linking reaches its gel point or more, and described is super Molecule hydrogen bond crosslinks are participated in realizing by side hydrogen bond group；Common covalent cross-linking is free of in 2nd network, but contains inorganic boric acid estersil Key dynamic covalent cross-linking does not contain the side hydrogen bond group.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network includes Common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein the common covalent cross-linking reaches its gel point or more, and described is super Molecule hydrogen bond crosslinks are participated in realizing by the side hydrogen bond group；Include common covalent cross-linking and inorganic boric acid silicon in 2nd network Ester bond dynamic covalent cross-linking, wherein the common covalent cross-linking reaches its gel point or more, does not contain the side hydrogen bond base Group.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is simultaneously Including common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reach its gel point with On, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include the side hydrogen Key acts on；Without covalently cross-linked in 2nd network, but polymer chain there are side hydrogen bond group and participates in forming hydrogen bond crosslinks.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is simultaneously Including common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reach its gel point with On, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include the side hydrogen Key acts on；Contain common covalent cross-linking and inorganic boric acid estersil key dynamic covalent cross-linking in 2nd network, but it does not contain the side Hydrogen bond group.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is simultaneously Including common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reach its gel point with On, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include the side hydrogen Key acts on；Contain inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen in 2nd network Key crosslinking is participated in realizing by the side hydrogen bond group.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is simultaneously Including common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reach its gel point with On, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include the side hydrogen Key acts on；2nd network includes common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalent Crosslinking reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, the supermolecule hydrogen bond Crosslinking includes the side hydrogen bond action；, but upper 1st and the 2nd network differs.
In yet another embodiment of the present invention, the dynamic aggregation object is made of three networks, is contained in the 1st network There are common covalent cross-linking and inorganic boric acid estersil key dynamic covalent cross-linking, but it does not contain the side hydrogen bond group；In 2nd network Without covalently cross-linked, but there are the side hydrogen bond groups on polymer chain, and form the hydrogen bond that the side hydrogen bond group participates in Crosslinking；3rd network is while including common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent Crosslinking reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, the supermolecule hydrogen bond Crosslinking includes the side hydrogen bond action.
In yet another embodiment of the present invention, the dynamic aggregation object is made of three networks, is contained in the 1st network There are inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen bond crosslinks are by the side hydrogen Key group participates in realizing, but does not contain common covalent cross-linking；Without covalently cross-linked in 2nd network, but exist on polymer chain The side hydrogen bond group, and form the hydrogen bond crosslinks that the side hydrogen bond group participates in；3rd network is while comprising common covalent Crosslinking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reaches its gel point or more, and described is dynamic State covalent cross-linking is realized that the supermolecule hydrogen bond crosslinks include the side hydrogen bond action by inorganic boric acid estersil key.
In yet another embodiment of the present invention, the dynamic aggregation object is made of three networks, is contained in the 1st network There are inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen bond crosslinks are by the side hydrogen Key group participates in realizing, but common covalent cross-linking is not present；2nd and the 3rd network is total comprising common covalent cross-linking, dynamic simultaneously Valence is crosslinked and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reaches its gel point or more, the dynamic covalent cross-linking by Inorganic boric acid estersil key realizes that the supermolecule hydrogen bond crosslinks include the side hydrogen bond action, but the 2nd and the 3rd network is not Together.
In yet another embodiment of the present invention, the dynamic aggregation object is made of three networks, and the 1st network is general Valence cross-linked network in all does not contain dynamic covalent bond and hydrogen bond；2nd network is dynamic covalent cross-linking network, is free of hydrogen bond crosslinks； 3rd network is the hydrogen bond crosslinks network that the side hydrogen bond group participates in, and is free of dynamic covalent cross-linking and common covalent cross-linking.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is general Valence cross-linked network in all does not contain dynamic covalent bond and hydrogen bond；2nd network is the hydrogen bond crosslinks net that the side hydrogen bond group participates in Network is free of dynamic covalent cross-linking and common covalent cross-linking；Non-crosslinked dynamic containing the covalent inorganic boric acid estersil key of dynamic is covalent Polymer is scattered in above-mentioned two network.
In yet another embodiment of the present invention, the dynamic aggregation object is made of two networks, and the 1st network is general Valence cross-linked network in all does not contain dynamic covalent bond and hydrogen bond；2nd network is dynamic covalent cross-linking network, is free of hydrogen bond crosslinks With common covalent cross-linking；Non-crosslinked supermolecule polymer containing side hydrogen bond action is scattered in above-mentioned two network.
In yet another embodiment of the present invention, the dynamic aggregation object is made of a network, and cross-linked network is Common covalent cross-linking network, without containing the covalently cross-linked and hydrogen bond crosslinks of dynamic；Contain the covalent inorganic boric acid estersil key of dynamic Non-crosslinked dynamic covalent polymer and non-crosslinked dynamic supermolecule polymer containing side hydrogen bond are scattered in above-mentioned network.
In yet another embodiment of the present invention, the dynamic aggregation object is made of a network, and cross-linked network is Common covalent cross-linking network, without containing the covalently cross-linked and hydrogen bond crosslinks of dynamic；Contain dynamic covalently inorganic boric acid estersil simultaneously The non-crosslinked dynamic aggregation object of key and side hydrogen bond is scattered in above-mentioned network.
In yet another embodiment of the present invention, the dynamic aggregation object is made of a network, and cross-linked network is Common covalent cross-linking network, and selectively contain the hydrogen bond crosslinks that the side hydrogen bond participates in；With the covalent inorganic boric acid silicon of dynamic The crosslinked dynamic covalent polymer of ester bond is scattered in granular form in the network, wherein containing the optional side hydrogen bond ginseng With hydrogen bond crosslinks.
In addition to the embodiment of above-mentioned 17 kinds of hybrid cross-linked network structures, the present invention can also have other diversified Hybrid cross-linked network structure embodiment those skilled in the art can be with logic according to the present invention and train of thought, rationally and effectively It realizes.
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 silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma refers to that silicone hydroxyl is contained in the end of compound And/or the compound that silicone hydroxyl presoma is any appropriate.The silicon-containing compound is selected from small molecule silicon-containing compound and macromolecular Silicon-containing compound can be organic or inorganic compound, including silica.The silicon-containing compound can have any appropriate Topological structure, including but not limited to line style, ring-type (include but not limited to monocycle, polycyclic, bridged ring, nested rings), it is branched (including But be not limited to combed, star-like, dendritic, hyperbranched type), two-dimensional/three-dimensional cluster, and combinations thereof form.
In embodiments of the present invention, the side hydrogen bond group is the hydrogen bond group on side group and/or side chain skeleton, It can be any appropriate hydrogen bond group.It is preferred that having hydrogen bond receptor and hydrogen-bond donor simultaneously in a side hydrogen bond group；It can also It is that part side hydrogen bond group contains hydrogen-bond donor, other part side hydrogen bond group contains hydrogen bond receptor；Most preferably simultaneously contain by Body and donor.
The receptor of heretofore described side hydrogen bond group preferably comprises structure at least one 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；Selected from arbitrary Suitable atom, group, segment, cluster；Wherein, R is selected from hydrogen atom, substitution atom, substituent group.
The donor of heretofore described side hydrogen bond group preferably comprises structure at least one shown in the following general formula (2),
Structure shown in general formula (1) and (2) can be side group, end group, linear chain structure, the branched chain structure containing side group, It can be cyclic structure etc..Wherein, the cyclic structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, Caged scaffold, nested ring structure etc..
In embodiments of the present invention, the side hydrogen bond group preferably contains structure shown in general formula (1) and (2) simultaneously. Implementation result according to the present invention, side hydrogen bond group preferably are selected from amide groups, carbamate groups, thiocarbamate base, urea Base, pyrazoles, imidazoles, imidazoline, triazole, purine, porphyrin and their derivative.
In embodiments of the present invention, the form of the dynamic aggregation object composition with hybrid cross-linked structure can be Ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid Body swell gel), foam etc..
In embodiments of the present invention, the dynamic aggregation object with hybrid cross-linked structure may be used also in preparation process It is blended with to be selectively added the other polymers that can be added/use, auxiliary agent, filler and collectively constitutes dynamic aggregation object.
Wherein, the other polymers that can be added/use are selected from following any or appoint several：Natural polymer, Synthetic resin, synthetic rubber, synthetic fibers；
Wherein, the auxiliary agent that can be added/use is selected from following any or appoints several：Catalyst, initiator, antioxidant, light Stabilizer, heat stabilizer, crosslinking agent, curing agent, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming Agent, dynamic regulation agent, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, Rheological agent, thickener, levelling agent；
Wherein, the filler that can be added/use is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, Organic filler.
In embodiments of the present invention, the dynamic aggregation physical performance with hybrid cross-linked structure is adjustable on a large scale, It has broad application prospects, specifically, can be applied to and make damper, padded coaming, acoustic material, noise elimination material Material, defense of resistance to impact material, athletic protective article, army and police's protective article, self-repairability coating, self-repairability plank, selfreparing The products such as property binder, bulletproof glass squeegee, toughness material, shape-memory material, toy, force snesor.
Compared with prior art, the invention has the advantages that：
(1) a kind of dynamic aggregation object with hybrid cross-linked structure of the invention combines common covalent cross-linking, dynamic altogether The inorganic boric acid estersil key of valence and supermolecule hydrogen bond, the advantages of making full use of and combine each bonding action.Wherein, common covalent It is crosslinked and provides the one strong network structure stablized for dynamic aggregation object, polymer can keep balanced structure namely size Stability；And introduce dynamic in the polymer covalently after inorganic boric acid estersil key and supermolecule hydrogen bond action, dynamic covalent bond and The dynamic of hydrogen bond can assign material excellent dynamic, including but not limited to weak bond characteristic and dynamic key characteristic, especially Dilatancy.Dynamic covalent bond and hydrogen bond energy are broken in the form of " can sacrifice key " under external force, a large amount of to dissipate Energy, enough toughness is provided for cross-linked polymer so that cross-linked polymer is to possess the intrinsic mechanics of cross-linked structure strong While degree and stability, also possess excellent tensile toughness and tear resistance；Its dilatancy can provide excellent for material Power dissipation and absorbability obtain the performances such as splendid damping, damping, shock resistance.And dynamic covalent bond and hydrogen bond are each other It is orthogonal, coordinate supplement, obtains ideal performance.This is only to contain individually a kind of bonding action therein not accomplishing 's.Based on dynamic, the difference of response and intensity between different bondings, the dynamic change of orthogonality/time sequence can be obtained With fracture/dissociation under response and stress, to obtain multiple response, energy absorption, the work(such as shape memory to the maximum extent Energy.This, which is the prior art, to provide.
(2) it is participated in comprising the side hydrogen bond group in a kind of dynamic aggregation object with hybrid cross-linked structure of the present invention Supermolecule hydrogen bond action, since the side hydrogen bond usually hangs on the side of main chain backbone, density, distribution, structure etc. side Face all has flexible adjustability, can easily regulate and control the glass transition temperature of polymer, and especially it participates in formation The glass transition temperature of hydrogen bond, and formed hydrogen bond dynamic etc., therefore have advantage outstanding.
(3) in a kind of dynamic aggregation object with hybrid cross-linked structure of the present invention, in addition to the side hydrogen bond, other party Face is also structure-rich, and performance is various.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 aggregation object with different structure, abundant different to make dynamic aggregation object reveal Performance, meet the application demand of different occasions.
(4) the present invention a kind of dynamic aggregation object with hybrid cross-linked structure in dynamic reversible key dynamic response By force, dynamic response mild condition.Compared to other existing dynamic covalent systems, the present invention takes full advantage of inorganic boric acid estersil Key have good thermal stability and high dynamic invertibity, can without catalyst, without the condition of high temperature, illumination or specific pH It is lower to realize that the synthesis of dynamic aggregation object and dynamic reversibility also reduce use environment while improving preparation efficiency Limitation extends the application range of polymer.In addition, by optionally controlling other conditions (as auxiliary agent, adjustment is added Reaction temperature etc.), it can accelerate or be quenched dynamic covalent chemical balance under appropriate environment, be at required state, This is more difficult inside existing supramolecular chemistry and dynamic covalent systems to accomplish.
(5) the dynamic aggregation object with hybrid cross-linked structure a kind of in the present invention reflects functional characteristic.Pass through tune Dynamic component in whole dynamic aggregation object can make polymeric acceptor reveal stimulating responsive and dilatancy, polymer can external force, It is made a response under the environmental stimulis such as temperature, pH, illumination, changes oneself state.The boric acid estersil key and supermolecule hydrogen of dynamic reversible Key can re-start bonding, so that material has plasticity, self-repairability after fracture by changing external condition Equal functional characteristics, while extending polymer service life, but also it can be applied to many special dimensions.
Specific implementation mode
The present invention relates to a kind of dynamic aggregation objects with hybrid cross-linked structure, wherein at least include a covalent cross-linking net The degree of cross linking of network, common covalent cross-linking therein reaches its gel point or more；Simultaneously comprising the covalent inorganic boric acid estersil key of dynamic The supermolecule hydrogen bond action participated in side hydrogen bond group.
Term " polymerization " (reaction) used 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 " (reaction) used in the present invention refers to passing through between reactant molecule and/or in reactant molecule Common covalent bond or the chemistry of dynamic covalent bond and/or the supramolecular chemistry of hydrogen bond connect to be formed with two dimension, three-dimensional cluster simultaneously And then form the process of three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain it is general first two-dimensional/three-dimensional direction not It is disconnected to increase, cluster (can be two dimension or three-dimensional) is gradually formed, developing deeply is three-dimensional infinite network.Unless stated otherwise, originally The three-dimensional infinite network structure of gel point or more (containing, similarly hereinafter) is refered in particular in crosslinking in invention, it is non-crosslinked include line style, it is branched, cyclic annular, Two-dimentional cluster and gel 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, and be not belonging to across The cross-linked network that can constitute an entirety of 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..
In embodiments of the present invention, " the dynamic covalent bond ", refers to inorganic boric acid estersil key.Wherein, institute The inorganic boric acid estersil key stated, any appropriate position that can be on polymer chain both can be in main polymer chain skeleton On, it can also be chained in polymer lateral chain and/or branch and/or bifurcated chain backbone and/or crosslinking.The present invention is also not precluded within Contain inorganic boric acid estersil key in the side group and/or end group of polymer chain.Since boron atom is trivalent structure, polymerization process generates The inorganic boric acid estersil can result in bifurcated and can be crosslinked in turn.The inorganic boric acid estersil key can be crosslinked , can also be on noncrosslinking polymer on polymer network, being also not excluded for can be in small molecule.
In the present invention, " skeleton " refers to structure on the chain length direction of polymer chain." main chain ", it is poly- to being crosslinked For closing object, the arbitrary segment being present in cross-linked network skeleton is referred to；For non-cross-linked polymer, such as non-specifically say It is bright, refer to the longest segment of chain link.Wherein, " side chain " refers to that same main polymer chain skeleton is connected and is distributed In the chain structure of main chain backbone side；Wherein, it can also be other from arbitrary that " branch "/" bifurcated chain ", which can be side chain, The chain structure that chain bifurcated comes out.Wherein, " side group " refers to that the arbitrary chain of same polymer is connected and is distributed in chain side Chemical group.For " side chain ", " branch " and " side group ", can have multilevel hierarchy namely side chain/branch that can continue band There are side group and side chain/branch, side chain/branch of side chain/branch that can continue have side group and side chain/branch.Wherein, described " end group " refers to that the arbitrary chain of same polymer is connected and is located at the chemical group of chain end.For hyperbranched and dendroid chain And its relevant branched chain structure, branch can also be considered as main chain, but in the present invention, then the branch of outermost is considered as branch Chain, rest part are considered as main chain.For the sake of simplicity, branch/bifurcated chain is accordingly to be regarded as side chain in the present invention.In the embodiment party of the present invention In formula, " the side hydrogen bond group " refers to the hydrogen bond group carried on polymer chain side group and/or side chain skeleton, can handed over It, can also be on noncrosslinking polymer on the polymer network of connection.The side hydrogen bond group can be formed with side hydrogen bond group Hydrogen bond action can also form hydrogen bond action with the hydrogen bond group on main polymer chain skeleton, can also be with organic/inorganic filler The hydrogen bond group on surface forms hydrogen bond action, can also form hydrogen bond action with the hydrogen bond group in auxiliary agent/additive/solvent, But the present invention not only limits and this, and the supermolecule hydrogen bond action that these side hydrogen bond groups participate in can be referred to as side hydrogen bond (effect).This Invention can also include the hydrogen bond action other than the hydrogen bond action of side, including but not limited to main chain backbone hydrogen bond group and main chain backbone Hydrogen bond action, main chain backbone hydrogen bond group between hydrogen bond group and the hydrogen bond action between end group hydrogen bond group.According to hydrogen bond Situations such as quantity of group, structure and distribution, hydrogen bond action can be polymerization, ring formation in chain, interchain linkage effect, Grafting, side group functionalization, preferred polymeric acts on, ring formation, interchain linkage act in chain.Side hydrogen bond group is in structure and performance Aspect has great flexibility, therefore can assign the dynamic aggregation object performance that other hydrogen bond actions are unable to reach.
According to the embodiment of the present invention, a covalent cross-linking network is included at least in the dynamic aggregation object, it is therein Common covalent cross-linking reaches in gel point or more namely dynamic aggregation object comprising common covalent friendship more than at least one gel point Networking network；Dynamic covalent cross-linking and/or supermolecule hydrogen bond crosslinks can also be contained in the network of this covalent cross-linking.Described is dynamic Can also include one or more common covalent cross-linking networks in state polymer in addition to this at least one common covalent cross-linking network And/or the network of dynamic covalent cross-linking and/or supermolecule hydrogen bond crosslinks.Dynamic covalently inorganic boric acid estersil key and/or be based on side The supermolecule hydrogen bond action of hydrogen bond group can be on cross-linked network, can not also be total on cross-linked network, namely containing dynamic The ingredient of the inorganic boric acid estersil key of valence and/or the supermolecule hydrogen bond action based on side hydrogen bond group can be noncrosslinking (gel Or less), it can not be on the network of common covalent cross-linking.It is preferred that dynamic covalently inorganic boric acid estersil key and/or be based on side hydrogen The supermolecule hydrogen bond action of key group participates in crosslinking, more preferably with common covalent cross-linking on the same cross-linked network.
In embodiments of the present invention, the common covalent cross-linking in the same dynamic polymer systems can have it is a kind of or Person more than one, you can with using any appropriate common covalent cross-linking topological structure, chemical constitution, reactive mode and combinations thereof Deng.In embodiments of the present invention, the cross-linked network in a dynamic polymer systems at least one, you can be single One network, it is possibility to have the multiple networks being mutually blended, it is possibility to have multiple networks of interpenetrating can also exist simultaneously blending With interpenetrating, etc.；Wherein, two or more networks can be identical or different；Can be subnetwork only include it is common covalently Crosslinking and subnetwork only include the combination of inorganic borate key and/or side hydrogen bond crosslinks, or part only includes common Covalent cross-linking and part include the combination of common covalent cross-linking and inorganic borate key and/or side hydrogen bond crosslinks simultaneously, either Part only includes that inorganic borate key and/or side hydrogen bond crosslinks and part include common covalent cross-linking and inorganic borate key simultaneously And/or side hydrogen bond crosslinks combination or each network in all simultaneously include common covalent cross-linking and inorganic borate key And/or side hydrogen bond crosslinks, but the present invention is not limited only to this.Crosslinking in single one network can be common covalent cross-linking, move The combination of one or more of state covalent cross-linking, hydrogen bond crosslinks.For the polymer of the present invention, the common covalently friendship Be associated at least one network and reach gel point or more, can ensure in this way even if only there are one network in the case of, polymerization Object can also keep balanced structure, namely can be (at least partly) the insoluble solid not melted in the normal state.When depositing In multiple networks, can there are interaction, namely dynamically covalent and/or supermolecular mechanism between heterogeneous networks, it can also phase It is mutually independent.
In an embodiment of the invention, only there are one networks (for the dynamic aggregation object of the hybrid cross-linked network A kind of network structure), which is characterized in that include common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond simultaneously in network Crosslinking.Wherein, the common covalent cross-linking is realized by common covalent bond, and common covalent cross-linking reaches the solidifying of common covalent cross-linking It is more than glue point；The dynamic covalent cross-linking is realized by inorganic boric acid estersil key；The supermolecule hydrogen bond crosslinks include side hydrogen Key acts on.Present network architecture is the simplest, but can merge three kinds of different bonding patterns simultaneously in one network, realizes Best quadrature-synergy effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (second of network structure), which is characterized in that the 1st network includes common covalent cross-linking and dynamic covalent cross-linking, wherein described Common covalent cross-linking reaches its gel point or more；The dynamic covalent cross-linking realized by inorganic boric acid estersil key, side group and The side hydrogen bond group is not contained on side chain.It is crosslinked without common covalent bond and inorganic boric acid estersil key in 2nd network, but poly- It closes and there are side hydrogen bond group and participates in hydrogen bond crosslinks in the side group and/or side chain skeleton of object chain；In the network structure, pass through the 1st Common covalent cross-linking in network keeps balanced structure and inorganic boric acid estersil key therein to provide covalent dynamic, by the Side hydrogen bond crosslinks in 2 networks provide supermolecule dynamic.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the third network structure), which is characterized in that the 1st network includes common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein described Common covalent cross-linking reach its gel point or more；The supermolecule hydrogen bond crosslinks by be present in polymer chain side group and/or Side hydrogen bond group on side chain skeleton participates in realizing.Common covalent cross-linking is free of in 2nd network, but containing by inorganic boric acid estersil The dynamic covalent cross-linking that key is formed does not contain the side hydrogen bond group in side group and side chain.In the network structure, pass through Common covalent cross-linking in 1 network keeps balanced structure, and covalently dynamic is provided by the inorganic boric acid estersil key in the 2nd network Property, provide supermolecule dynamic by the side hydrogen bond crosslinks in the 1st network.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 4th kind of network structure), which is characterized in that the 1st network includes common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein described Common covalent cross-linking reach its gel point or more；The supermolecule hydrogen bond crosslinks by be present in polymer chain side group and/or Side hydrogen bond group on side chain skeleton participates in realizing.Include common covalent cross-linking and inorganic boric acid estersil key dynamic in 2nd network Covalent cross-linking, wherein the common covalent cross-linking reaches its gel point or more, and the side is not contained in side group and side chain Hydrogen bond group.In the network structure, balanced structure is kept by common covalent cross-linking in the 1st network and the 2nd network, by the Inorganic boric acid estersil key in 2 networks provides covalent dynamic, and supermolecule dynamic is provided by the side hydrogen bond crosslinks in the 1st network Property.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 5th kind of network structure), which is characterized in that the 1st network is the first described network structure；It is handed over without covalent bond in 2nd network Connection, but there are side hydrogen bond group and participate in forming hydrogen bond crosslinks on the side group of polymer chain and/or side chain skeleton.The network structure In, keep balanced structure and inorganic boric acid estersil key therein to provide covalent dynamic by the covalent cross-linking in the 1st network；It is logical The side hydrogen bond crosslinks crossed in the 1st and the 2nd network provide supermolecule dynamic.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 6th kind of network structure), which is characterized in that the 1st network is the first described network structure；Containing common covalent in 2nd network Crosslinking and inorganic boric acid estersil key dynamic covalent cross-linking, but the side hydrogen bond group is not contained on its side group and side chain.The net In network structure, balanced structure and inorganic boric acid estersil therein are kept by the common covalent cross-linking in the 1st network and the 2nd network Key provides covalent dynamic；Supermolecule dynamic is provided by the side hydrogen bond crosslinks in the 1st network.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 7th kind of network structure), which is characterized in that the 1st network is the first described network structure；Contain inorganic boric acid in 2nd network Estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen bond crosslinks are by being present in polymer chain side group And/or the side hydrogen bond group on side chain skeleton participates in realizing.In the network structure, by common in the 1st network and the 2nd network Covalent cross-linking keeps balanced structure and inorganic boric acid estersil key therein to provide covalent dynamic；Pass through the 1st network and the 2nd network In side hydrogen bond crosslinks supermolecule dynamic is provided.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 8th kind of network structure), which is characterized in that the 1st network and the 2nd network are the structure described in the first network, but upper described 1st and the 2nd network differs.It is this to differ, the crosslinking for example, polymer chain agent structure difference, covalent cross-linking can be lifted The hydrogen bond group of density difference, polymer chain side group and/or side chain formed on different, polymer chain side group and/or side chain is not On an equal basis.In the embodiment, by adjusting the structure of the 1st network and/or the 2nd network, it can reach and accurately control dynamic aggregation The purpose of physical performance.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of three networks (the 9th kind of network structure), which is characterized in that covalent containing common covalent cross-linking and inorganic boric acid estersil key dynamic in the 1st network Crosslinking, but the side hydrogen bond group is not contained on its side group and side chain；In 2nd network altogether without common covalent cross-linking and dynamic Valence is crosslinked, but there are side hydrogen bond groups on the side group of polymer chain and/or side chain skeleton, and is participated in by the side hydrogen bond group Form hydrogen bond crosslinks；3rd network is the first described network structure.In the network structure, pass through the 1st network and the 3rd network In common covalent cross-linking keep balanced structure and inorganic boric acid estersil key therein to provide covalent dynamic, pass through the 2nd and the 3rd Side hydrogen bond crosslinks in network provide supermolecule dynamic.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of three networks (the tenth kind of network structure), which is characterized in that contain inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen in the 1st network Key is crosslinked, and the supermolecule hydrogen bond crosslinks are real by the side hydrogen bond group being present on polymer chain side group and/or side chain skeleton It is existing, but do not contain common covalent cross-linking；Common covalent cross-linking and dynamic covalent cross-linking, but polymer chain are free of in 2nd network There are side hydrogen bond groups in side group and/or side chain, and participate in forming hydrogen bond crosslinks by the side hydrogen bond group；3rd network is The first described network structure.In the network structure, balanced structure is kept by the common covalent cross-linking in the 3rd network, is led to The inorganic boric acid estersil key crossed in the 1st and the 3rd network provides covalent dynamic, passes through the side hydrogen bond in the network of the 1st, the 2nd and the 3rd Crosslinking provides supermolecule dynamic.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of three networks (a kind of the tenth network structure), which is characterized in that contain inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule in the 1st network Hydrogen bond crosslinks, the supermolecule hydrogen bond crosslinks are by being present in the side hydrogen bond group on polymer chain side group and/or side chain skeleton It realizes, but common covalent cross-linking is not present；2nd and the 3rd network is described the first network structure, but the 2nd and the 3rd network It is different.In the network structure, balanced structure and nothing therein are kept by the common covalent cross-linking in the network of the 1st, the 2nd and the 3rd Machine boric acid estersil key provides covalent dynamic, and supermolecule dynamic is provided by the side hydrogen bond crosslinks in the 1st and the 3rd network.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of three networks (the 12nd kind of network structure), which is characterized in that the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen Key；2nd network is dynamic covalent cross-linking network, is free of hydrogen bond crosslinks；3rd network is that the side hydrogen bond group participates in the hydrogen to be formed Key cross-linked network is free of dynamic covalent cross-linking and common covalent cross-linking.Three networks are not only respectively independent but also cooperate with mutually.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 13rd kind of network structure), which is characterized in that the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen Key；2nd network is that the side hydrogen bond group participates in the hydrogen bond crosslinks network to be formed, and is covalently handed over common without dynamic covalent cross-linking Connection；Non-crosslinked dynamic covalent polymer containing the covalent inorganic boric acid estersil key of dynamic is scattered in above-mentioned two network.1st net Network is for providing balanced structure, and the 2nd network is for providing the crosslinking of dynamic supermolecule, and noncrosslinking dynamic covalent polymer is for carrying For additional viscosity.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 14th kind of network structure), which is characterized in that the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen Key；2nd network is dynamic covalent cross-linking network, is free of hydrogen bond crosslinks and common covalent cross-linking；Non- friendship containing side hydrogen bond action Connection supermolecule polymer is scattered in above-mentioned two network.For 1st network for providing balanced structure, the 2nd network is dynamic for providing State covalent cross-linking, noncrosslinking dynamic supermolecule polymer is for providing additional viscosity.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of a network (the 15th kind of network structure), which is characterized in that cross-linked network is common covalent cross-linking network, covalently cross-linked without containing dynamic And hydrogen bond crosslinks；Containing the dynamically non-crosslinked dynamic covalent polymer of covalent inorganic boric acid estersil key and contain the non-friendship of side hydrogen bond Linkage state supermolecule polymer is scattered in above-mentioned network.Common covalent cross-linking network is noncrosslinking for providing balanced structure Dynamic is covalently and supermolecule polymer is for providing additional viscosity.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of a network (the 16th kind of network structure), which is characterized in that cross-linked network is common covalent cross-linking network, covalently cross-linked without containing dynamic And hydrogen bond crosslinks；Non-crosslinked dynamic aggregation object simultaneously containing the covalent inorganic boric acid estersil key of dynamic and side hydrogen bond is scattered in above-mentioned In network.Common covalent cross-linking network is for providing balanced structure, and noncrosslinking dynamic is covalently and supermolecule polymer is for carrying For additional viscosity.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of a network (the 17th kind of network structure), which is characterized in that cross-linked network is common covalent cross-linking network, and selectively contains the side The hydrogen bond crosslinks that hydrogen bond participates in；With dynamic, covalently the inorganic crosslinked dynamic covalent polymer of boric acid estersil key disperses in granular form In above-mentioned network, wherein the hydrogen bond crosslinks participated in containing the optional side hydrogen bond.Common covalent cross-linking network is for providing Balanced structure, crosslinked dynamic covalent polymer are dispersed in cross-linked network for providing additional viscosity and strong with grain shape Degree.
In addition to the embodiment of above-mentioned 17 kinds of hybrid cross-linked network structures, the present invention can also have other diversified Hybrid cross-linked network structure embodiment can include three or its above identical or different net in one embodiment Network can include different common covalent cross-linkings and/or different dynamic covalent cross-linkings and/or different hydrogen in the same network Key is crosslinked, and can disperse/fill non-cross-linked polymer ingredient or friendship containing dynamic covalent bond and/or side hydrogen bond in network structure The particle (including but not limited to fiber, sheet and any suitable irregular shape) of connection.In special circumstances, covalent cross-linking net Side hydrogen bond group in network itself cannot form mutually hydrogen bond, need to form hydrogen bond with the other compositions being additionally added into.It is inorganic Boric acid estersil key is for providing covalent dynamic property, including but not limited to plasticity, self-repairability and dilatancy；Side hydrogen bond group On the one hand the hydrogen bond action of formation provides additional intensity for polymer as reversible physical crosslinking, on the one hand can utilize again Its good dynamic property assigns the performances such as stress/strain response, ultra-tough, selfreparing, shape memory.The skill of this field Art personnel can rationally and effectively be realized with logic according to the present invention and train of thought.
In the present invention, the quantity of the side hydrogen bond group of polymer and distribution are not limited.Particularly, when covalent cross-linking There are when the side hydrogen bond group in network, the quantity of the side hydrogen bond group on polymer segment between two covalent cross-linking points It is not also limited with distribution, can contain the side hydrogen bond group on the segment between any two covalent cross-linking point, Can also be to contain side hydrogen bond group on the segment between partial cross-linked point；The covalent cross-linking point containing side hydrogen bond group it Between segment on, preferably each segment contains no less than 2 side hydrogen bond groups, and more preferably each segment contains no less than 5 A side hydrogen bond group；Quantity of the side hydrogen bond group in entire covalent cross-linking network does not also limit, preferably average Containing no less than 0.1 side hydrogen bond group on segment between each described two covalent cross-linking points, further preferably not Less than the 1 side hydrogen bond group.
Based on the dynamic and response of the dynamic covalently inorganic boric acid estersil key and hydrogen bond, dynamic aggregation of the invention Object can show diversified dynamic property and the response performance for environmental stimuli, including but not limited to self-repairability, Temperature-responsive, stress/strain response, especially dilatant performance.When the inorganic boric acid estersil key and hydrogen bond not with it is general Logical covalent cross-linking collective effect and when the two collective effect does not generate crosslinked polymer yet, even if dynamic polymer systems are being answered Dilatancy energy occurs under power/effects of strain, does not contribute elastic property, and only promotes the viscosity of system, this phenomenon is advantageous In passing through viscous loss mechanical energy.When the degree of cross linking of any type in the inorganic boric acid estersil key and hydrogen bond reaches its gel Or more but it is wherein another simultaneously when forming independent non-cross-linked polymer, dynamic polymer systems are reached when dilatant occurs Visco-elastic conversion or elasticity enhancing will occur for the effect more than to gel point, and gel point effect below will promote viscosity, The destruction of external force is effectively reduced while the viscous loss to external force can occur in this way.When the inorganic boric acid estersil key and hydrogen When the degree of cross linking of key reaches its gel point or more, dynamic polymer systems will only occur visco-elastic and turn when dilatant occurs It changes or elasticity enhances, the partial cohesive loss to external force can occur in this way can reduce external force to the maximum extent again simultaneously It destroys.Different situations respectively have feature and advantage.
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".
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, refer to compound structure in contain silicon hydroxyl Base and/or any appropriate compound of silicone hydroxyl presoma.The silicon-containing compound is selected from small molecule silicon-containing compound and big point Sub- silicon-containing compound can be organic or inorganic compound, including silica.The silicon-containing compound can have arbitrary conjunction Suitable topological structure, including but not limited to line style, ring-type (including but not limited to monocycle, polycyclic, bridged ring, nested rings), branched (packet Include but be not limited to combed, star-like, dendritic, hyperbranched type), two-dimensional/three-dimensional cluster, and combinations thereof form.One dynamic is total Can be there are many silicon-containing compound in valence polymer, but the silicon-containing compound of the present invention must satisfy at least partly described dynamic Hydrogen bond group is carried on covalent polymer.
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 the present invention, the silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma can be any appropriate contains The compound of end group and/or side group silicone hydroxyl and/or silicone hydroxyl presoma, including small molecule and macromolecular compound, wherein connecting Group or segment that group or segment containing silicone hydroxyl and/or silicone hydroxyl presoma can be any appropriate are connect, including but unlimited In carbon-based/carbon-chain structure, the miscellaneous base of carbon/carbon heterochain structure, carbon base/carbon chain structure, the miscellaneous miscellaneous element chain of element base/carbon of carbon Structure, element base/element chain structure, miscellaneous element base/miscellaneous element chain structure.Wherein carbon-based/carbon-chain structure refers to group/chain Skeleton is only made of carbon atom；The miscellaneous base of carbon/carbon heterochain structure refers to also containing miscellaneous original on group/chain backbone outside carbon atom Son, wherein hetero atom include but not limited to oxygen, nitrogen, sulphur；Carbon base/carbon chain structure refers to removing on group/chain backbone Also contain Elements Atom outside carbon atom, wherein Elements Atom includes but not limited to P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir； The miscellaneous miscellaneous element chain structure of element base/carbon of carbon refers to also containing hetero atom and pantogen on group/chain backbone outside carbon atom Son；Element base/element chain structure refers to only contains Elements Atom on group/chain backbone；Miscellaneous element base/element heterochain structure, It refers to only containing Elements Atom and hetero atom in group/chain structure.
The suitable silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma can be exemplified below, and the present invention is not It is only limitted 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 Silicon-containing compound combine and generate Inorganic Boron acid estersil key, it is preferred to use inorganic boric acid and the macromolecular chemical combination containing silicone hydroxyl The macromolecular compound, inorganic borate (salt) and the macromolecular containing silicone hydroxyl of object, inorganic boric acid and siliceous hydroxyl groups precursors Object is closed to form inorganic boric acid estersil key, more preferably uses inorganic boric acid and macromolecular compound, inorganic boric acid containing silicone hydroxyl Ester forms inorganic boric acid estersil key with the macromolecular compound containing silicone hydroxyl, more preferably using inorganic borate and containing silicone hydroxyl Macromolecular compound form inorganic boric acid estersil key.
In embodiments of the present invention, the dynamic aggregation can be obtained by generating inorganic boric acid estersil key Object, can also first preparing the compound containing the inorganic boric acid estersil key, polymerized/cross-linked/blending is described dynamic to generate again State polymer.In the present invention, the polyvalency based on Si atoms, on the silicon-containing compound containing linker a participation form B-O- The Si atoms of Si can at most form three B-O-Si, share a Si atom；And since boron atom is trivalent structure, gather The inorganic boric acid estersil that conjunction process generates can be easy to cause to form bifurcated and can be crosslinked in turn.
In the present invention, in addition to silicon-containing compound, other any raw materials, dynamic aggregation object ingredient any polymer/chain Section can have any appropriate topological structure, and 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 has side group, side chain, branch, and side group, side chain, branch It can continue, with side group, side chain, branch, can also have multilevel hierarchy.
In embodiments of the present invention, the number of teeth of hydrogen bond is not limited.If the number of teeth of hydrogen bond is more, intensity is big, So dynamic of hydrogen bond crosslinks can play with regard to weak and promote dynamic aggregation object to keep balanced structure and improve mechanical property (mould Amount and intensity) effect.If the number of teeth of hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond crosslinks, can be with dynamic covalently with regard to strong Inorganic boric acid estersil key provides dynamic property, such as self-repairability, energy absorption characteristics together.In embodiments of the present invention, excellent Choosing is used as crosslinking no more than the hydrogen bond of four teeth.
The number of teeth is donor (D, that is, hydrogen atom) and the receptor (A, that is, receive hydrogen atom by side hydrogen bond group Electronegative atom) the hydrogen bond quantity that constitutes, each D-A is combined as a tooth and (is shown below, lists a tooth, two teeth respectively With the hydrogen bond bonding situation of three tooth hydrogen bond groups).
In embodiments of the present invention, the side hydrogen bond group can be any appropriate hydrogen bond group.It is preferred that one There are hydrogen bond receptor and hydrogen-bond donor simultaneously in the hydrogen bond group of side；Can also be that part side hydrogen bond group contains hydrogen-bond donor, in addition Part side hydrogen bond group contains hydrogen bond receptor；Most preferably contain receptor and donor simultaneously.
The receptor of heretofore described side hydrogen bond group preferably comprises at least one in structure shown in the following general formula (1) Kind,
Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Selected from arbitrary Suitable atom, group, segment, cluster；Wherein, R is selected from hydrogen atom, substitution 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, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl 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, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20It is fat miscellaneous alkyl, miscellaneous Aryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20It 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 C1-20Alkyl, substitution C1-20Alkenyl, substituted aryl, substituted aryl, substituted C1-20Fat miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl hydrocarbon Base, substituted C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, substituted aryl sulphur The C of base carbonyl substitution1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl alkylthio carbonyl Any atom or group in base, substituted artyl sulfo thiocarbonyl etc..Wherein, butyl includes but not limited to normal-butyl, uncle 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 Substituent group, containing any in heteroatomic substituent group.
The donor of heretofore described side hydrogen bond group preferably comprises at least one in structure shown in the following general formula (2) Kind,
Structure shown in general formula (1) and (2) can be side group, end group, linear chain structure, the branched chain structure containing side group, It can be cyclic structure etc..Wherein, the cyclic structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, Caged scaffold, nested ring structure etc..
In embodiments of the present invention, the side hydrogen bond group preferably contains structure shown in general formula (1) and (2) simultaneously. Implementation result according to the present invention, side hydrogen bond group preferably are selected from amide groups, carbamate groups, thiocarbamate base, urea Base, pyrazoles, imidazoles, imidazoline, triazole, purine, porphyrin and their derivative.
Side hydrogen bond group in suitable side group and/or side chain (including branch/bifurcated chain) skeleton is lifted for example, but the present invention It 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 shorter than 20, more preferably Less than 5.
End group hydrogen bond group can be consistent with the side hydrogen bond group.In addition, suitable cross-linked network skeleton and non-crosslinked Main chain backbone hydrogen bond group on main chain backbone can lift for example, but the present invention be not limited only to this：
In the present invention, it can contain in same polymer and have more than a kind of above-mentioned side hydrogen bond group, the same network In can also contain and have more than a kind of above-mentioned side hydrogen bond group, other optional hydrogen bond groups can also be contained.To that can import The compound of the side hydrogen bond group and other optional hydrogen bond groups is not particularly limited, and is correspondingly formed the hydrogen bond group Reaction type and mode etc. are also not particularly limited.Such as：Pass through carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanide Covalent reaction between acid esters group and amino is formed；By covalent anti-between isocyanate groups and hydroxyl, sulfydryl, carboxyl It should be formed；It is formed by the covalent reaction between succinimide group and amino, hydroxyl, sulfydryl.
In the present invention, the supermolecule hydrogen bond crosslinks in cross-linked network can have any appropriate degree of cross linking, Ke Yi It more than its gel point, can also be below its gel point.The supermolecule hydrogen bond crosslinks can be in dynamic aggregation object into action It is generated during state covalent cross-linking；Can also be to be generated in advance after supermolecule hydrogen bond crosslinks again into Mobile state covalent cross-linking； Supermolecule hydrogen bond crosslinks, but this hair can be generated during dynamic aggregation object subsequent forming after dynamic covalent cross-linking is formed It is bright to be not limited only to this.
In embodiments of the present invention, the form of the dynamic aggregation object composition with hybrid cross-linked structure can be Ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid Body swell gel), foam etc., wherein the dissolvable small-molecular-weight component content contained in ordinary solid and solid foam is general Not higher than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Ordinary solid has intensity High advantage, shape and volume are relatively more fixed, and density is big, are suitable for the anti-explosion wall or apparatus housings of high intensity；Elastomer General properties with ordinary solid, but elasticity is more preferable, and pliability is more preferable, has better damping, damping, sound insulation, noise elimination etc. Energy absorption performance；Gel has the advantages that softness, there is preferable energy absorption capacity and elasticity, is suitable for preparing the energy-absorbing material of high-damping； And foam then has many advantages, such as that low density, lightweight, specific strength are high, soft foam material also has good elasticity and energy absorption capacity.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.
In the preparation process of dynamic aggregation object expanded material, mainly using mechanical foaming method, physical blowing method, chemistry hair Three kinds of methods of bubble method foam to dynamic aggregation object.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be gelled, cures and become foamed material.For shorten molding cycle can be passed through air and be added emulsifier or Surfactant.
Wherein, the physical blowing method, be realized using physical principle in the preparation process of dynamic aggregation object it is poly- The foaming for closing object, generally comprises following five kinds of methods：(1) inert gas blown method, i.e., inert gas under pressurized condition It is pressed into molten polymer or pasty material, then decompression heating, makes the gas expansion of dissolving and foam；(2) low boiling point is utilized Liquid evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, keep liquid molten Enter in polymer beads, then heat and soften polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching uses liquid Body medium, which immerses in polymer, dissolves the solid matter added in advance, makes to occur a large amount of holes in polymer and be in foaming Shape, such as by solable matter salt, starch elder generation and mixed with polymers, put in water after being shaped to product, then by product It handles repeatedly, solable matter is dissolved out to get to open-celled foam product；(4) hollow microsphere method is added in the polymer Become obturator-type foam through solidification after hollow microsphere；(5) freeze-drying is initially formed gel or swelling body, then carries out Freeze-drying obtains foam.Wherein, it is sent out preferably by the method for dissolving in inert gas and low-boiling point liquid in the polymer Bubble.Using physical blowing method, has and operate the advantages that Poisoning is smaller, and foaming raw material cost is relatively low, foaming agent noresidue body.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally comprise following two methods：(1) thermal decomposable foaming agent foaming utilizes chemical foaming agent The gas decomposed to give off after heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, that is, utilize hair The chemical reaction occurred between two or more components in foam system, generating inert gas (such as carbon dioxide or nitrogen) causes Polymer is expanded and is foamed.Polymerisation and foamable reaction balance carry out in order to control in foaming process, to ensure that product has preferably Quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by adding in the polymer The method of chemical foaming agent is added to foam.
In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to be molded dynamic aggregation object foamed material.
Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material is direct plungeed into die cavity to carry out foaming；Two-step method refers to first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam is molded ratio Two-step method is easy to operate and production efficiency is high, therefore it is preferred that one-step method carries out moulded from foam molding.
Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve In certain flow rate injecting material melt, then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent Under the action of form nuclei of bubbles.After expansion stage and solidifying and setting stage are all happened at full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while making foam solidifying and setting with the cooling of mold.
Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.Since it can not only realize continuous production, and it is more more competitive than injection-expansion molded in cost, because This is current most widely used foaming technology.
In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is half open-celled structure that leading to again, which has mutual disconnected structure then,.It, also can be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes：(1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be more than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are more than 0.4g/cm3, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm3, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm3, expansion ratio is more than 9.
Be used to prepare the composition of raw materials component of dynamic aggregation object, except the inorganic compounds of boron and silicon-containing compound it Outside, further include the other polymers that can be added/use, auxiliary agent, filler, these can add/using object can be blended, participation The form reacted is learned with the reaction product of inorganic compounds of boron and silicon-containing compound collectively as dynamic with hybrid cross-linked structure State polymer formulators component, or play the role of improvement processing performance in the preparation process of dynamic aggregation object.
The other polymers added/used can play improvement material as additive in system Material new capability can, be assigned, materials'use and economic benefit is improved, has the function that material comprehensively utilizes.It can add/use Other polymers can be selected from natural polymer, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to being added Polymer character and possessed molecular weight do not limit, can be oligomer, Huo Zhegao according to the difference of molecular weight Polymers can be homopolymer or copolymer according to the difference of polymeric species, in the specific use process should be according to target material The performance of material and the needs of actual fabrication process and selected.
When the other polymers that can be added/use be selected from natural polymer when, can be selected from it is following any or Appoint several natural polymers：Natural rubber, chitosan, chitin, native protein etc..
When the other polymers that can be added/use are selected from synthetic resin, it can be selected from following any or appoint several conjunctions At resin：Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), Medium density polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, Polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- carbon Acid esters, dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane are total Polymers, polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, highly resistance Rush polystyrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetate Vinyl ester copolymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride- Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP) etc..
When the other polymers that can be added/use are selected from synthetic rubber, it can be selected from following any or appoint several conjunctions At 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 that can be added/use are selected from synthetic fibers, it can be selected from following any or appoint several conjunctions At fiber：Viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane are fine Dimension, polyacrylonitrile fibre, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..
In the preparation process of polymer material, the preferred natural rubber of other polymers that can add/use, polyethylene, Polypropylene, vinyl-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, Epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, second third Rubber, 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 for adding/using is selected from following any Kind appoints several auxiliary agents：Additive synthesis, including catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat are steady Determine agent；Improve the auxiliary agent of mechanical property, including chain extender, toughener, coupling agent；Improve the auxiliary agent of processing performance, including lubrication Agent, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent.
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 for adding/using, can cause monomer molecule in polymerization process It activates and generates free radical, improve reaction rate, reaction is promoted to carry out, include but are not limited to following any or appoint several draw Send out agent：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, peroxide Change bis- (4- tert-butylcyclohexyls) esters of two dicyclohexyl carbonates, dicetyl peroxydicarbonate, tert butyl peroxy benzoate, tertiary butyl Peroxidating pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred peroxidating of initiator Lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1-1wt%.
Antioxidant in the auxiliary agent for adding/using can delay the oxidation process of polymer samples, ensure Material can be carried out successfully preparing processing and extend its service life, included but are not limited to following any or appointed several anti- Oxygen agent：Hinered phenols, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyls Base phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl- 6- tert-butyl phenols]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros are equal Triazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent for adding/using can prevent polymer samples from light aging occurs, and extend Its service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide Titanium, zinc oxide, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxies two Benzophenone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzo three Azoles, 2,4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethyls Own ester；Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as Bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl esters), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light Stabilizer, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2, 2,6,6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- bis- uncles Butyl benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, N '-di-n-butyl dithiocarbamates Nickel formate etc.；Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent for adding/using enables to polymer samples processing or using Chemical change does not occur because heated in journey, or delays these variations to achieve the purpose that prolong the service life comprising but It is not limited only to following any or appoints several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, disalt Base lead stearate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, two Alkali lead phthalate, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, hard Resin acid calcium, lead stearate, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, tin dilaurate di-n-octyl Tin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital Tin C-102, dimercapto acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptans type Salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxyfatty acid Ester, epoxy resin；Phosphorous acid esters, 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 phosphite ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Wherein, The preferred barium stearate of heat stabilizer, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat used Stabilizing agent dosage is not particularly limited, generally 0.1-0.5wt%.
Crosslinking agent in the auxiliary agent, cooperation need to carry out crosslinked reactant composition progress in dynamic aggregation object It uses, bridging action can be played between the polymer molecule of line style, so that multiple linear molecules is mutually bonded and be cross-linked into reticular structure, The crosslink density and cross-link intensity that polymer can be further increased improve the heat resistance and service life of polymer, simultaneously Improve the mechanical performance and weatherability of material comprising but be not limited only to following any or appoint several crosslinking agents：Polypropylene glycol Glycidol ether, zinc oxide, aluminium chloride, aluminum sulfate, chromic nitrate, ethyl orthosilicate, methyl orthosilicate, p-methyl benzenesulfonic acid, to first Benzene sulfonyl chloride, diacrylate -1,4- butanediol esters, ethylene glycol dimethacrylate, butyl acrylate, aluminium isopropoxide, acetic acid Zinc, titanium acetylacetone, aziridine, isocyanates, phenolic resin, hexamethylenetetramine, cumyl peroxide, peroxidating bay Acyl, peroxidating stearoylketene, benzoyl peroxide, cyclohexanone peroxide, benzoyl peroxide ethyl ketone, di-t-butyl peroxide, adjacent benzene mistake Oxygen dicarboxylate, isopropyl benzene hydroperoxide, three tert-butyl peroxy base silane of vinyl ,-two tert-butyl peroxy base silicon of diphenyl Alkane, trimethyl t-butyl peroxy silane etc..Wherein, the preferred cumyl peroxide of crosslinking agent (DCP), benzoyl peroxide (BPO), peroxidating 2,4 dichloro benzene formyl (DCBP).Dosage of crosslinking agent used is not particularly limited, generally 0.1- 5wt%.
Curing agent in the auxiliary agent, cooperation need to carry out cured reactant composition progress in dynamic aggregation object It uses, can promote or control the curing reaction of reactant composition in the course of the polymerization process comprising but be not limited only to following any Kind appoints several curing agent：Amine curing agent, as ethylenediamine, diethylenetriamine, triethylene tetramine, dimethylaminopropylamine, six times Tetramine, m-phenylene diamine (MPD)；Acid anhydride type curing agent, such as phthalic anhydride, maleic anhydride, pyromellitic acid dianhydride；Amide Class curing agent, such as Versamid；Imidazoles, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles；Trifluoro Change boron complex etc..Wherein, the preferred ethylenediamine of curing agent (EDA), diethylenetriamine (DETA), phthalic anhydride, maleic Dicarboxylic anhydride, hardener dose used are not particularly limited, generally 0.5-1wt%.
Chain extender in the auxiliary agent for adding/using, can be with the reaction-ity group reaction on reactant molecule chain And make strand extension, molecular weight increase, be commonly used for preparing addible polyurethane/polyurea comprising but be not limited only to Under it is any or appoint several chain extenders：Polyalcohols chain extender, such as ethylene glycol, propylene glycol, diglycol, glycerine, three hydroxyls Methylpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, hydroquinone two hydroxy ethyl ether (HQEE), the double hydroxyls of resorcinol Ethylether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, as diaminotoluene, diamino dimethylbenzene, tetramethyl are sub- Xylylene diamine, tetraethyl diphenyl methylene diamines, tetra isopropyl hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminos Methyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiands (MOCA), 3,5- dimethyl sulphur-based first Phenylenediamine (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1,3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcohol Amine chain extender, such as triethanolamine, triisopropanolamine, N, bis- (2- hydroxypropyls) aniline of N '-.Chain extender dosage used is without spy It does not limit, generally 1-20wt%.
Toughener in the auxiliary agent for adding/using can reduce polymer samples brittleness, increase toughness, carry High material bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-fourth two Alkene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, propylene Nitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, benzene Ethylene-butadiene-styrene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene (ABS) copolymerization Object (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), methyl methacrylate-butadiene-styrene copolymerization Resin (MBS), chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent for adding/using, can improve polymer samples and inorganic filler or increasing The interface performance of strong material, reduces the viscosity of material melt in plastic processes, improves the dispersion degree of filler and is added with improving Work performance, and then product is made to obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any Kind appoints several coupling agents：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-(2,3- epoxies third Oxygen) propyl trimethoxy silicane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5- 2wt%.
Lubricant in the auxiliary agent for adding/using can improve the lubricity of polymer samples, reduce and rub It wipes, reduce Interface Adhesion performance comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbons Class, such as solid paraffin, microcrystalline wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, it is such as stearic Acid, hydroxy stearic acid；Fatty acid ester, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax； Aliphatic amide type, such as stearmide or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylenes are double stearic Amide；Fatty alcohol and polyalcohols, 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.Lubricant quantity used is not particularly limited, generally 0.5-1wt%.
Releasing agent in the auxiliary agent for adding/using, it can make polymer samples be easy to demould, surface is smooth, It is clean comprising but be not limited only to following any or appoint several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon Oil, methyl phenyl silicone 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 for adding/using, can increase the plasticity of polymer samples so that polymerization Hardness, modulus, softening temperature and the brittle temperature of object decline, and elongation, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fat Fat esters of gallic acid, 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 fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyls) oneself Ester, epoxy soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box acetylated castor oil Sour methyl esters；Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, 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), adjacent benzene Dibutyl carboxylic acid (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), O-phthalic Sour diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Foaming agent in the auxiliary agent for adding/using can make polymer samples foaming pore-forming, to obtain matter Gently, heat-insulated, sound insulation, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.
Dynamic regulation agent in the auxiliary agent for adding/using can be promoted and adjust dynamic aggregation object dynamic, with Just the expected performance of optimization is obtained, is usually that either free carboxyl group or can provide or receive electricity with free hydroxyl The compound of son pair, includes but are not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc.. Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt%.
Antistatic agent in the auxiliary agent for adding/using can draw the deleterious charge assembled in polymer samples It leads or eliminates, make it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several Antistatic agent：Anionic antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethyl Alcohol amine 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, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkane Base dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, N- lauryls- Bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol epoxy It is ethane additive product, fatty acid ethylene oxide addition product, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, sweet Oily mono fatty acid ester；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyene propionamide N- seasons such as ethylenediamine Ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, the preferred lauryl of antistatic agent Trimethyl ammonium chloride, octadecyldimethyl ethoxy quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used is not particularly limited, generally 0.3-3wt%.
Emulsifier in the auxiliary agent for adding/using can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitutes the surface tension between phase, is allowed to form uniform and stable dispersion or emulsion, is preferred for carrying out lotion Polymerized/cross-linked comprising but be not limited only to following any or appoint several emulsifiers：Anionic, such as higher fatty acid salt, alkane Base sulfonate, alkylbenzene sulfonate, Negel, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor Sesame oil sulfuric acid, sulphation butyl ricinoleate salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, as alkylammonium salt, Alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic Type, as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide add At object, fatty acid glyceride, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, alcohol Amine fatty acid amide etc.；Wherein, the preferred neopelex of emulsifier, sorbitan fatty acid ester, triethanolamine are stearic Acid esters (Emulphor FM).Emulsifier used is not particularly limited, generally 1-5wt%.
Dispersant in the auxiliary agent for adding/using enables to solid flocculation group point in mixed with polymers liquid It dissipates and is suspended in liquid for tiny particle, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, simultaneously Also it can prevent the sedimentation and cohesion of particle, be formed and stabilize suspension comprising but be not limited only to following any or appoint several points Powder：Anionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as fat Fat alcohol polyoxyethylene ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Wherein, divide The preferred neopelex of powder, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.Point used Powder dosage is not particularly limited, generally 0.3-0.8wt%.
Colorant in the auxiliary agent for adding/using, can make polymeric articles show required color, Increase surface color and polish comprising but be not limited only to following any or appoint several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium Red, iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalein Cyanines are red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, intellectual circle Blue RSN, slag rhodamine toner, Oil Yellow etc.；Wherein, the selection of colorant, need not be special depending on color sample demand It limits.Colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent for adding/using can make contaminated substance obtain the glittering of similar fluorite Luminous effect comprising but be not limited only to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, Pyrazoline type, benzo oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent Bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of (fluorescent brightener CBS), 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 for adding/using when incident light being enabled to reach polymer surfaces, occurs Diffusing reflection generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents：It is heavy Barium sulfate, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc. drop；Wherein, the preferred dioxy of delustering agent SiClx.Delustering agent dosage used is not particularly limited, generally 2-5wt%.
Fire retardant in the auxiliary agent for adding/using, can increase the flame resistance of material comprising but not only limit In following any or several fire retardants：Phosphorus system, as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, Phosphate toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Have Machine halide, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；It is inorganic fire-retarded Agent, such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos Propyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, and one As be 1-20wt%.
Nucleating agent in the auxiliary agent for adding/using can accelerate knot by the crystallization behavior of change polymer Brilliant rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, the raising product transparency, The purpose of the physical mechanical properties such as lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, packet It includes but is not limited only to following any or appoints several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid Sodium, silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, nucleating agent is preferred Silica, benzylidene sorbitol (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
It is good can to ensure that polymer has during film for rheological agent in the auxiliary agent for adding/using Brushability and coating thickness appropriate, prevent storage when solid particle sedimentation, its redispersibility can be improved comprising but It is not limited only to following any or appoints several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, carbonic acid Calcium, lithium chloride, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound is such as hard Resin acid aluminium, aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanic acid Ester derivant, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferably organic swelling of rheological agent Soil, polyethylene wax, hydrophobically modified alkalinity swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used It is not particularly limited, generally 0.1-1wt%.
Thickener in the auxiliary agent for adding/using, can assign the good thixotropy of mixed with polymers liquid and Consistency appropriate, to meet various need such as its stability and application performance during production, storage and use It asks comprising but be not limited only to following any or appoint several thickeners：Lower-molecular substance, such as fatty acid salt, alkyl dimethylamine It is oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, sweet Oily trioleate, coamidopropyl glycine betaine, titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, micro mist Silica, colloidal aluminum, animal protein, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid are total Polymers, polyacrylamide, polyvinyl pyrrolidone, polyethers etc.；Wherein, the preferred hydroxyl coconut oil diethanol amide of thickener, acrylic acid- Methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the auxiliary agent for adding/using can ensure that the flat smooth of polymer coating film is uniform, change Kind film coated surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Poly dimethyl silicon Oxygen alkane, polymethylphenylsiloxane, polyacrylate, organic siliconresin etc.；Wherein, the preferred polydimethylsiloxanes of levelling agent Alkane, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
In the preparation process of dynamic aggregation object, auxiliary agent preferred catalyst, initiator, antioxidant, the light that can add/use Stabilizer, heat stabilizer, chain extender, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.
The filler primarily serves following effect in dynamic aggregation object：1. reducing the shrinking percentage of moulded products, carry Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjusting the viscosity of polymer； 3. meeting different performance requirement, such as raising polymer material impact strength and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The 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：Skin Hair, natural rubber, asbestos, shellac, chitin, chitosan, protein, raw lacquer, shell powder, silk, artificial silk, phenolic aldehyde microballon, tree Fat microballon etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, chitosan, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
It, can be by any appropriate material hybrid mode known in the art by one in the preparation process of dynamic aggregation object Surely the raw material matched prepares dynamic aggregation object by mixing, and can be interval, semicontinuous or continuous processing form mixing； Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic aggregation object.The hybrid mode packet of use Include but be not limited only to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., wherein it is preferred that Solution is stirred, melting is stirred and melting extrusion.Energy in material mixed process provides form It is limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, injection moulding, mould Molded, tape casting, calendering formation, cast molding.
In the preparation process of dynamic aggregation object, can also be added the foregoing description the other polymers added/used, / use auxiliary agent, can add/filler used can be added to collectively constitute dynamic aggregation object compound system, but these additives It is not necessarily all necessary.
The specific method for preparing dynamic aggregation object, the typically shape by raw material to dissolve or disperse are stirred using solution Formula is stirred mixing in the reactor in respective solvent or in common solvent.In general, hybrid reaction temperature controls At 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, time control is mixed in 0.5-12h, preferably 1-4h.It can incite somebody to action The product obtained after mixing is poured into suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0- 48h obtains polymer samples.It can select during this to retain as needed existing for solvent is made in the form of paste, glue etc. Polymer samples, or selection remove solvent and solid polymer sample existing for the forms such as membranaceous, blocky, foam-like are made.With When the method prepares dynamic aggregation object, usually also need to that initiator is optionally added in a solvent in a manner of polymerisation in solution to draw Hair polymerization obtains dynamic aggregation object, or addition dispersant and oil-soluble initiator are configured to suspension with suspension polymerisation or slurry The mode of polymerization obtains dynamic aggregation object to cause polymerization, or addition initiator and emulsifier are configured to emulsion and are gathered with lotion The mode of conjunction obtains dynamic aggregation object to cause polymerization.Used polymerisation in solution, suspension polymerisation, slurry polymerization and lotion are poly- The method of conjunction, is well known to those skilled in the art and widely used polymerization, can be adjusted according to actual conditions It is whole, it is no longer 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 aggregation is prepared using deionized water Object simultaneously selects when being retained, and can obtain hydrogel；Dynamic aggregation object is prepared using organic solvent and selects to be retained When, organogel can be obtained；When preparing dynamic aggregation object using oligomer and selecting to be retained, oligomer can be obtained Swell gel；When preparing dynamic aggregation object using plasticizer and selecting to be retained, plasticizer swell gel can be obtained；Profit When preparing dynamic aggregation object with ionic liquid and selecting to be retained, ionic liquid swell gel can be obtained.
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.
It is stirred the specific method for preparing dynamic aggregation object using melting, typically directly stirs raw material in the reactor It is stirred reaction after mixing mixing or heating melting, such mode is generally gas, liquid or lower melting-point solid in raw material In the case of use.In general, the control of hybrid reaction temperature is at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixing is stirred Time control is mixed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, in 0- 150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, polymer samples are obtained.Dynamic aggregation object is prepared in this approach When, it usually also needs to be optionally added into a small amount of initiator to cause in a manner of melt polymerization or gas-phase polymerization polymerization and obtains dynamic Polymer.The method of its used melt polymerization, gas-phase polymerization, is well known to those skilled in the art and is widely used Polymerization, can be adjusted according to actual conditions, no longer be developed in details here.
The specific method of dynamic aggregation object is mixed with using melting extrusion, be typically add the raw material into extruder into Row squeezes out blending reaction, and extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be cut into conjunction after direct tape casting Suitable size either carries out obtained extrusion sample to utilize injection molding machine or moulding press to carry out sample preparation after being crushed.Injection temperature is 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature be 0-280 DEG C, preferably 25-150 DEG C, more It is preferred that 25-80 DEG C, clamp time 0.5-60min, preferably 1-10min, the preferred 4-15MPa of molding pressure.Batten can be placed in In suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, final polymer samples are obtained.
In the preparation process of dynamic aggregation object, mole of selected inorganic compounds of boron and (poly-) silicone compounds Equivalent proportion should be at range appropriate, preferably 0.1~10 range, more preferable 0.3~3 range, more preferable 0.8~1.2 Range.In actual fabrication process, those skilled in the art can be adjusted according to actual needs.
In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The dynamic aggregation physical performance is adjustable on a large scale, has broad application prospects, in military aerospace equipment, function Coating and the fields such as coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material all have important answer With.
Based on dilatancy, dynamic possessed by dynamic aggregation object, the dynamic aggregation object has excellent energy absorption performance, Can absorb and reduce including mechanical energies such as vibration, vibrations, impact, explosion, sound waves, thus using the dynamic aggregation object as Energy-absorbing material can be used as effective energy-absorbing method, can be applied to making damping shock absorber, for various motor vehicles, machine The vibration isolation of tool equipment, bridge, building, for polymer material when vibrated, the big energy that can dissipate plays damping effect Fruit, to effectively mitigate vibrations；Also it can be applied to amortizing packaging material, athletic protective system as energy-absorbing buffering material Product, the police protective materials of surge guard product and army etc., it is suffered under external force to reduce article or human body Vibrations and impact, include noise and the shock wave etc. that explosion generates；As energy-absorbing material, sound insulation, noise elimination etc. can also be carried out. Using the bond energy intensity and dynamic sex differernce of dynamic covalent bond and hydrogen bond, can also be used as shape-memory material, When the external force is removed, the deformation that material generates in loading procedure can be restored.
By dynamic reversibility possessed by dynamic aggregation object and rate of stressing dependence, the poly- of stress sensitive type is prepared Object material is closed, a part can be applied to prepare the magic toy and body-building material with stress/strain response, it may also be used for system Speed lockup's device of standby road and bridge can be also used for making antidetonation shear plate or pulsating stress carrying tool, or be used for Make stress monitoring sensor.
The had dynamic of dynamic aggregation object is made full use of, the binder with self-repair function can be prepared, is applied In the gluing of various types of materials, bulletproof glass squeegee also can be used as；It can also be used for preparing the polymer envelope with good plasticity Stifled glue, can design and prepare the scratch resistant coatings with part self-repair function, to extend the service life of coating, realize Long-effective corrosion protection to basis material.Huge application potential is shown in the fields such as military project, space flight, electronics, bionical.
It is carried out using inorganic boric acid estersil key and hydrogen bond as key can be sacrificed in use, it can pass through order under external force Property fracture, general hydrogen bond is first broken then inorganic boric acid estersil key fracture, absorbs a large amount of energy and assign polymer material With excellent toughness, it is hereby achieved that the polymer material that toughness is splendid, be widely used in military affairs, space flight, movement, the energy, The fields such as building.
Dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specific implementation Example is present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
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 1a。
1,5- hexadiene -3- alcohol and ethyl isocyanate are mixed according to equimolar ratio, using triethylamine as catalyst, It is reacted in dichloromethane, obtains the compound 1b that side group carries carbamate groups.
By compound 1a, compound 1b and trimethylolpropane tris (2- mercaptoacetates) according to molar ratio 1:1:2 carry out Mixing adds 1wt% organobentonites, the concussion of 1wt% bentonite after mixing, is placed on ultraviolet radioactive in UV crosslinking instrument 8h obtains a kind of dynamic aggregation object containing common covalent cross-linking, boric acid estersil key and side hydrogen bond group.
The polymeric articles can as with certain energy absorption characteristics and with tear resistance sheet material or coating make With.
Embodiment 2
Side group carries organopolysiloxane (molecular weight about 8000), 5- mercaptomethyl uracils, the 3- of terminal olefin group Mercaptopropyl trimethoxysilane and 1,12- dimercaptos dodecane according to double bond and the compound of each sulfydryl molar ratio 22:10: 10:1 mixing is added the photoinitiator benzoin dimethylether (DMPA) of 0.2wt% and is placed in UV crosslinking instrument after stirring fully Ultraviolet radioactive 4h obtains that a kind of organopolysiloxane containing common covalent cross-linking and side hydrogen bond group is prepared.
The above-mentioned organopolysiloxane containing side hydrogen bond group and trimethylborate are according to Si-OCH3Group and B-OR groups Molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, and is added dropwise to a small amount of acetic acid, then add Enter 5wt% Graphene powders, concussion after mixing, carries out polymerisation under stirring, is prepared a kind of containing common The dynamic aggregation object of covalent cross-linking, side hydrogen bond group and boric acid estersil key.
Large deformation can occur under smaller pressure or tensile force effect for the polymeric articles, but in Rapid stretching or fall But it can show high resiliency when beating, the variation and generation significant changes that conductivity can be with pressure or pulling force can be used as power Sensor.
Embodiment 3
(1) by poly dimethyl containing hydrogen silicone oil (molecular weight 6000) and 5- hexenyls trimethoxy silane, two allyl of adipic acid Ester mixes, in control reaction in poly dimethyl containing hydrogen silicone oil the molal quantity of active hydrogen atom (hydrogen atom being directly connected with Si) with The ratio of double bond molal quantity is about 10:9:1, addition reaction occurs using chloroplatinic acid as catalyst, obtained side group contains common total Valence is crosslinked and the organopolysiloxane of trimethoxy group.
By organopolysiloxane obtained above and boric acid according to Si-OCH3The molar ratio 1 of group and B-OH groups:1 is mixed It closes, is heated to 60 DEG C and reaction 16h is carried out by stirring, it is poly- to obtain a kind of dynamic containing common covalent cross-linking and boric acid estersil key Object is closed, as the 1st network polymer.
(2) N- allyls -1H- benzimidazolyl-2 radicals-amine and basudin -2,4 5- butane -2- base -5- propyl- 2- alkenyl -1,3-, 6- triketones are 10 according to molar ratio:10:3 mixing, swell in the 1st network polymer, and 5wt% carbon nanotubes, ultrasound is added 5min adds the AIBN of 5mol% as initiator, is heated to 80 DEG C of reaction 8h, one kind is made by free radical polymerization and contains The dynamic aggregation object of common covalent cross-linking, side hydrogen bond group and boric acid estersil key.
The polymeric articles have excellent toughness, can prepare and block glue, squeegee as polymer.
Embodiment 4
(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 compound is prepared.
By above-mentioned disiloxane compound and boric acid according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, adds Heat carries out reaction 8h to 60 DEG C by stirring, a kind of dynamic aggregation object containing boric acid estersil key is obtained, as the 1st network polymerization Object.
(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 4a 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 4b containing thio carbamate groups.
Olefinic monomer 4a, olefinic monomer 4b and allyl sulfide in molar ratio 50:50:3 are sufficiently mixed, and 80 parts of rings are added Oxygen soybean oil swells in the 1st network polymer after stirring is sufficiently mixed, adds the AIBN of 5mol%, pass through radical polymerization It is poly- that a kind of dynamic of the epoxy soybean oil swell containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key is prepared in conjunction Close object organogel.
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 is applied to defense of resistance to impact.
Embodiment 5
(1) bis- chloro- 1,1,3,3,5,5,7,7,9,9,11,11- of 1,11-, ten dimethyl, six siloxanes and boric acid are according to silicon hydroxyl The molar ratio 3 of base and borate:2 mixing, are added dropwise to 20% a small amount of acetic acid aqueous solution, after being stirred evenly under the conditions of 50 DEG C, 6h is reacted, a kind of dynamic aggregation object containing boric acid estersil key is prepared, as the 1st network polymer.
(2) 5- vinyl-2-pyrrolidones, trihydroxymethyl propane ethoxy ester triacrylate in molar ratio 20:1 is fully mixed It closes, is dissolved in 1- butyl -3- methylimidazole hexafluorophosphates ([C4MIM]PF6) ionic liquid, the AIBN of 5mol% is added as drawing Agent is sent out, is allowed to fully swell in the 1st network polymer, after stirring is sufficiently mixed, pours into the glass template die for accompanying silica gel pad In tool, it is placed on ultraviolet radioactive 10h in UV crosslinking instrument, you can obtain a kind of dynamic containing side hydrogen bond group and boric acid estersil key Polymer ions liquid gel.
Above-mentioned dynamic aggregation object ionic liquid gel is displaced into ionic liquid through deionized water, and is gone every 12h replacements Ionized water is primary, replaces 4 times to get a kind of dynamic aggregation containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key Object hydrogel.
The modulus of hydrogel prepared by the embodiment is in 13kPa, and strain can reach 15 times, and fracture strength is in 69kPa.It should Hydrogel can be used for the amortizing packaging material of breakables.
Embodiment 6
(1) poly- (dimethyl-methylphenyl) siloxanes of end silicone hydroxyl, isopropanol pinacol borate are according to silicone hydroxyl and boron The molar ratio 1 of acid esters:1 mixing, is added dropwise to 20% a small amount of acetic acid aqueous solution, after being stirred evenly under the conditions of 50 DEG C, reacts 8h, A kind of dynamic aggregation object containing boric acid estersil key is prepared, as the 1st network polymer.
(2) diallyl aminomethoxy antifebrin, Lu's succinimide mercaptans, trimethylolpropane tris (3-thiopropionate) According to molar ratio 20:20:1 mixing, is added in 120wt% plasticizer epoxidized methyl acetorieinoleates and adds 0.2wt% Benzoin dimethylether (DMPA), stirring be sufficiently mixed after, take 50g mixtures to swell in the 1st network polymers of 50g, then plus Enter the Fe of 1.6g surface modifications3O4Particle and 1.0g bentonite, ultrasonic 5min make Fe3O4Particle is uniformly dispersed wherein, then falls In the glass board mould for entering to accompany silica gel pad, be placed on ultraviolet radioactive 8h in UV crosslinking instrument, one kind containing common covalent cross-linking, The organogel that the epoxidized methyl acetorieinoleate of hydrogen bond group and boric acid estersil key is swollen.
For the modulus of the organogel of epoxidized methyl acetorieinoleate swelling prepared by the embodiment in 20kPa, strain can To reach 15 times, fracture strength is in 100kPa.This organogel can be used for preparing airborne and air-drop defense of resistance to impact material Material.
Embodiment 7
(1) poly- (dimethyl-methylphenyl) siloxanes of end silicone hydroxyl and three (4- chlorphenyls) borates according to silicone hydroxyl and The molar ratio 1 of borate:2 mixing, are added dropwise to 20% a small amount of acetic acid aqueous solution, after being stirred evenly under the conditions of 50 DEG C, reaction A kind of dynamic aggregation object containing boric acid estersil key is prepared, as the 1st network polymer in 8h.
(2) limonene oxide extracted from orange peel, and 100psi carbon dioxide, under the catalytic action of beta-diimine zinc Polymerisation occurs, obtains makrolon PLimC.
By above-mentioned makrolon PLimC and 2- aminoothyl mercaptans, 2- t-butoxycarbonyl aminos ethyl mercaptan according to double bond group It is 10 with sulfydryl ratio:5:5 mixing, are added the AIBN of 0.3wt%, and polymerization obtains a kind of side group and contains amino and carbamate The makrolon of base.
Two fourth of tin dilaurate of 0.2wt% is added in the makrolon that above-mentioned side group contains amino and carbamate groups 1st network polymer of Ji Xi, 0.2wt% triethylenediamine, the polymer foaming microballoon of 4wt% and 80wt%, is fully stirred It mixes uniformly, finally adds the hexamethylene diisocyanate of 20wt%, quickly stirred through professional equipment to bubble is generated, then It is injected into mold rapidly, cures 30min at room temperature, then cure 4h at 80 DEG C and covalently handed over containing common to get to one kind The binary interpenetrating networks composite foam material of connection, side hydrogen bond 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, and have toughness and durability, while having good biodegradable Property.
Embodiment 8
(1) acetyl bromide of acrylic acid 2- amino-ethyls ester and equimolar equivalent is dissolved in dichloromethane, is catalyzed in triethylamine Under obtain the olefinic monomer 8a of amide bond.
4- amino -3,5- difluoros phenethyl ester 1.0g, potassium permanganate 8.5g, green vitriol 8.6g are dissolved in 30mLDCM is refluxed overnight, and obtains azobenzene product.Above-mentioned azobenzene product 0.81g, 1,6- hexylene glycol 4.8g, 0.03gK2CO3, It is dissolved in 14mLDMSO, reacts 9h at 60 DEG C, obtain the hydroxyl azobenzene in end.The hydroxyl azobenzene of above-mentioned end 0.72g, addition 1.84mL triethylamine, 3mgDMAP are dissolved in the anhydrous DCM of 5mL, are added 0.6mL methacrylic chlorides, are reacted Night obtains the azobenzene 8b of alkadienes.
By the olefinic monomer 8a of polymethyl hydrogen siloxane (PHMS, molecular weight 8000) and above-mentioned amide bond, alkadienes Azobenzene 8b mixing, active hydrogen atom (hydrogen atom being directly connected with Si) rubs in poly dimethyl containing hydrogen silicone oil in control reaction The ratio of double bond molal quantity is about 10 in your number and 8a, 8b:9:1, addition reaction occurs using chloroplatinic acid as catalyst, side is made Base contains the organopolysiloxane of hydrogen bond group, as the 1st network polymer.
(2) side group with terminal olefin group organopolysiloxane (molecular weight about 6000) and 1,4- dimercaptos butane, 3- mercaptopropyl trimethoxysilanes according to double bond and the compound of two sulfydryls molar ratio 20:2:16 mixing, are added 0.2wt% Photoinitiator benzoin dimethylether (DMPA), stirring fully after, be placed on ultraviolet radioactive 4h in UV crosslinking instrument, be prepared one Organopolysiloxane of the kind containing common covalent cross-linking and side hydrogen bond group.
Above-mentioned organopolysiloxane and boric acid are 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 100mL1- butyl -3- methylimidazole hexafluorophosphates ([C is added4MIM]PF6) ionic liquid, it is fully molten It is swollen then to be added dropwise to 20% a small amount of acetic acid solution in the 1st network, polymerisation is carried out under stirring, and one kind is prepared High strength ionic liquid dynamic aggregation object gel containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key.
The modulus of the ionic liquid gel can reach 32 times in 36kPa, strain, and fracture strength is in 200kPa.This product It can be used in fine mold as stress loading material, while playing the role of bearing stress, and be had centainly Deformability plays cushioning effect.
Embodiment 9
(1) side group carries the organopolysiloxane (molecular weight about 3000) and 4'4- dimercapto diphenyl sulfides of terminal olefin group Ether, 3- mercaptopropyl trimethoxysilanes according to double bond and the compound of two sulfydryls molar ratio 2:1:1 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 common covalent cross-linking is prepared.
The above-mentioned organopolysiloxane containing common covalent cross-linking and 2,6- di-tert-butyl -4- tolyl dibutyl original boron Acid esters according to terminal siloxane and borate molar ratio 1:1 mixing, be warming up to 80 DEG C after mixing, be added 4ml go from Sub- water is added dropwise to a small amount of acetic acid, and polymerisation is carried out under stirring, and one kind is prepared and contains side hydrogen bond group and boron The dynamic aggregation object of sour estersil key, as the 1st network polymer.
(2) 4,5- dihydros -2- vinyl -1H- imidazoles, 1- (3- pyrrolidinyls) -2- propylene -1- ketone, hex- 1,5- diene - 3,4- diketone is 10 according to molar ratio:10:1 mixing, swells in the 1st network polymer, the AIBN for adding 1 molar equivalent is Initiator, and 5wt% titanium alloy powders, 5wt% ceramic powders, 10wt% calcium sulfate is added and is fully blended, it is heated to 80 DEG C of reactions It is poly- that a kind of dynamic containing common covalent cross-linking, a variety of side hydrogen bond groups and boric acid estersil key is made by free radical polymerization in 8h Close object.
The polymeric articles can be used as a kind of protecting against shock material.
Embodiment 10
(1) organopolysiloxane (molecular weight about 3000) and 5- mercapto methyl urine of the side group with terminal olefin group are phonetic Pyridine, four mercaptoacetate of pentaerythrite are according to double bond and the molar ratio of sulfydryl 100:96:1 mixing, is added the light-initiated of 0.2wt% Agent benzoin dimethylether (DMPA) is placed on ultraviolet radioactive 4h in UV crosslinking instrument after stirring fully, obtains one kind is prepared and contains There is the organopolysiloxane of side hydrogen bond group.
The above-mentioned organopolysiloxane containing side hydrogen bond group and 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids Ester according to terminal siloxane and borate molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, the deionization of 4ml is added Water carries out polymerisation under stirring, and one kind is prepared and contains common covalent cross-linking, side hydrogen bond group and boric acid estersil The dynamic aggregation object of key, as the 1st network polymer.
(2) 4,5- dihydros -2- vinyl -1H- imidazoles, 1- (3- pyrrolidinyls) -2- propylene -1- ketone are according to molar ratio 10:10 mixing, swell in the 1st network polymer, 1.0g montmorillonites, 1.2g carbon blacks, 0.35g di-iron trioxides are added, then add The AIBN for entering 1 molar equivalent is initiator, is heated to 80 DEG C and reacts 8h, is made a kind of containing common covalent by free radical polymerization It is crosslinked, the dynamic aggregation object of a variety of side hydrogen bond groups and boric acid estersil key.
The product shows good viscoplasticity, has good isolation vibrations and stress buffer effect, while also table Excellent hydrolytic resistance is revealed.
Embodiment 11
(1) limonene oxide extracted from orange peel, and 100psi carbon dioxide, under the catalytic action of beta-diimine zinc Polymerisation occurs, obtains makrolon PLimC.
By above-mentioned makrolon PLimC and γ-mercapto hydroxypropyl methyl dimethoxysilane, N- [(2- mercaptoethyls) amino first Acyl] propionamide, two (2- mercaptoethyls) adipate esters according to double bond group and sulfydryl ratio are 20:10:8:2 mixing, are added The poly- carbon containing common covalent cross-linking, side hydrogen bond group and silicone hydroxyl presoma is made by click-reaction by the AIBN of 0.6wt% Acid esters.
Weigh the makrolon and (the 2- methoxyl group second of 5g tri- that the above-mentioned side groups of 24g contain hydrogen bond group and silicone hydroxyl presoma Base) borate, it is thoroughly mixed uniformly, after being warming up to 80 DEG C, the deionized water of 10ml is added, is gathered under stirring Reaction is closed, a kind of dynamic aggregation object containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key is prepared, as the 1 network polymer.
(2) by boric acid and acrylic dimethylchlorosilane according to molar ratio 1:3 mixing, using triethylamine as catalyst, 80 12h is reacted at DEG C, and the boric acid estersil compound 11a that end carries double bond is prepared.
Two mercaptan of 16g polyethers is added in three-necked flask, 5.4g above-mentioned ends carry the boric acid estersil compound of double bond 11a, 2.0g triallylamine are swollen in the 1st network polymer, and the Cellulose nanocrystal and 0.3wt% of 6wt% is then added Neopelex, ultrasonic 20min, then it is placed on ultraviolet radioactive 8h in UV crosslinking instrument, it obtains a kind of containing common covalent It is crosslinked, the dual network interpenetrating dynamic aggregation object of side hydrogen bond group and boric acid estersil key.
The polymer is prepared into film, shows more excellent comprehensive performance, there is certain tensile strength and good Good tear resistance, and can largely be stretched.Such dynamic aggregation object can be applied to prepare function film, or It can be used as the pad pasting of automobile and furniture, also can be used as stretch wrappers and used, very scratch-resistant.
Embodiment 12
(1) using hydroxy-ethyl acrylate as monomer, hydroxyethyl acrylate is made by free radical polymerization, and (molecular weight is about 1000)。
By above-mentioned oligomeric hydroxyethyl acrylate and hexamethylene diisocyanate, 3- isocyanate group propyl trimethoxies Base silane mixing (is 2 by hydroxyl and isocyanates molar ratio:1.1:1.1, that is, it is slightly excessive to control isocyanates), made with triethylamine It for catalyst, reacts in methylene chloride, obtained side group contains the polyacrylate of trimethoxy silane group.
Above-mentioned side group contain trimethoxy silicon group polyacrylate and boric acid according to Si-OCH3Group and B-OH groups Molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, and polymerisation 8h is carried out under stirring, one kind is obtained and contains The dynamic aggregation object of boric acid estersil key, as the 1st network polymer.
(2) by trimethylborate and dimethyl methyl oxygroup -3- butine silane according to molar ratio 1:3 mixing, are heated to 60 DEG C After being dissolved by stirring, it is added a small amount of water the reaction was continued 4h, obtains a kind of trivinyl containing boric acid estersil key Close object 12a.
Isosorbide-5-Nitrae-diacetylene -3- alcohol and methyl isocyanate are mixed according to equimolar ratio, using triethylamine as catalyst, It is reacted in dichloromethane, obtains the compound 12b that side group carries carbamate groups.
By compound 12a, compound 12b and 1,8- diazido -3,5- dioxaoctanes according to molar ratio 1:1:2 carry out Mixing, swells in the 1st network, is added in plasticizer phthalic acid dioctyl ester, add relative to monomer 0.1wt%'s Catalyst CuBr (PPh3)3With three [(1- benzyls -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), stir after being sufficiently mixed, It is reacted 12 hours under room temperature, you can obtain a kind of organogel of dioctyl phthalate swelling.
In 22kPa, strain can reach the modulus of the organogel of dioctyl phthalate swelling prepared by the embodiment To 18 times, fracture strength is in 100kPa.This organogel can be used for preparing airborne and air-drop defense of resistance to impact material.
Embodiment 13
(1) polybutadiene and 2- t-butoxycarbonyl aminos ethyl mercaptan, thiopurine methyltransferase methyldiethoxysilane, 1,4- dibutyl disulfides Alcohol is 100 according to double bond and sulfydryl ratio:50:40:10 mixing, using DMPA as photoinitiator, ultraviolet light is light source, is passed through a little It hits reaction and the polybutadiene for containing side hydrogen bond group and siloxane group containing common covalent cross-linking, side group is made.
26g polybutadiene obtained above and 3.2g tri- (4- chlorphenyls) borate are weighed, 60 DEG C is heated to and passes through stirring After being dissolved, it is added a small amount of 20% acetic acid aqueous solution the reaction was continued 4h, is obtained a kind of containing common covalent cross-linking, side hydrogen bond The dynamic aggregation object of group and boric acid estersil key, as the 1st network polymer.
(2) 2,3- dimercapto propionic acid and aniline are reacted according to equimolar ratio, add condensing agent dicyclohexylcarbodiimide (DCC) and activator 4-N, N- lutidines (DMAP) it, is stirred at room temperature for 24 hours, compound 13a can be made.
By a kind of methyl phenyl vinyl polysiloxanes (molecular weight 10000) and mercapto ethyl trimethoxy silane, compound 13a is 100 according to double bond and sulfydryl ratio:80:20 mixing, add 3g white carbons, 4g titanium dioxides, 1.3g di-iron trioxides, It swells in the 1st network polymer, the photoinitiator benzoin dimethylether (DMPA) of 0.4wt% is added and is placed on after stirring fully Ultraviolet radioactive 4h in UV crosslinking instrument is obtained being prepared and a kind of being contained common covalent cross-linking, side hydrogen bond group and boric acid estersil The dual network interpenetrating dynamic aggregation object of key.
The polymer samples have larger sticky and very good tensile toughness, can largely be stretched and Not broken (elongation at break is up to 600%).In the present embodiment, can make polymer as electronic package material or adhesive With avoiding damage to and gas leakage.
Embodiment 14
(1) it is single with methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and trimethylol-propane trimethacrylate Body, the molar ratio for controlling the two are 10:1, by free radical polymerization be made methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and The copolymer of trimethylol-propane trimethacrylate (molecular weight is about 2800).
By above-mentioned copolymer and trimethylborate according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, heating After mixing to 80 DEG C, the deionized water of 4ml is added, polymerisation is carried out under stirring, one kind is prepared and contains The dynamic aggregation object of common covalent cross-linking and boric acid estersil key, as the 1st network polymer.
(2) methacrylic acid 2- anilino-s ethyl ester, tert-butyl acrylate are 10 according to molar ratio:5 mixing, add 1 The AIBN of molar equivalent is initiator, is heated to 80 DEG C of reaction 8h, and being made a kind of by free radical polymerization contains side hydrogen bond group Dynamic aggregation object, as the 2nd network polymer.
(3) 4- allyls -1,6- heptadiene -4- alcohol and methyl isocyanate are mixed according to equimolar ratio, are made with triethylamine It for catalyst, reacts in methylene chloride, obtains the compound 14a that side group carries carbamate groups.
By boric acid and dimethyl methyl oxygroup -3- heptene silane according to molar ratio 1:3 mixing, be heated to 60 DEG C by stir into After row dissolving, it is added a small amount of water the reaction was continued 4h, obtains a kind of trivinyl compound 14b containing boric acid estersil key.
Two mercaptan of 1,3- diphenyl propanes -2,2- and by compound 14a, compound 14b according to molar ratio 1:1:3 are mixed It closes, then swells in again in the 1st network polymer and the 2nd network polymer, be placed on ultraviolet radioactive 8h in UV crosslinking instrument, obtain A kind of dynamic aggregation object containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key.
The polymeric articles can be used for preparing a kind of police protective materials of army.
Embodiment 15
(1) using methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and methacrylic acid 2- anilino-s ethyl ester as monomer, The molar ratio of both control is 10:6, methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and methyl are made by free radical polymerization The copolymer of acrylic acid 2- anilino- ethyl esters (molecular weight is about 4000).
By above-mentioned copolymer and triethyl borate according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, heating After mixing to 80 DEG C, the deionized water of 4ml is added, polymerisation is carried out under stirring, one kind is prepared and contains The dynamic aggregation object of side hydrogen bond group and boric acid estersil key, as the 1st network polymer.
(2) a certain amount of 5- cyclo-octene -1,2- glycol and 2- imidazolidinone -4- carboxylic acids are mixed, both control molal quantity Ratio be about 1:2, using bicyclic ethyl carbodiimide and 4-dimethylaminopyridine as catalyst, dichloromethane is solvent, is obtained The monomer 15a of hydrogen bonds group.
The monomer 15a of a certain amount of hydrogen bonds group and cyclo-octene are mixed, the ratio of both control molal quantity is about 1: 2, using Grubbs bis- generations catalyst as catalyst, using dichloromethane as solvent, obtain the pungent based on polycyclic of side group hydrogen bonds group Alkene polymer.
It is removed after 100 mass parts of above-mentioned polymer and 6 mass parts of cumyl peroxide are sufficiently mixed in methylene chloride Mixture is placed in mold and is heated to 150 DEG C and is kept for 2 hours by solvent, obtained after cooling side group hydrogen bonds group based on poly- The dynamic aggregation object of cyclo-octene, as the 2nd network polymer.
(3) with methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and 2- (1H- imidazol-4 yls) ethyl methacrylate Ester, two three (1,2-PD) diacrylates of contracting are monomer, and the molar ratio for controlling three is 10:4:1, pass through free radical polymerization Methacrylic acid 3- (trimethoxy silicon substrate) propyl ester, 2- (1H- imidazol-4 yls) ethylmethyl acrylates and two contractings three are made The copolymer (molecular weight is about 6600) of (1,2- propylene glycol) diacrylate.
By above-mentioned copolymer and trimethylborate according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, then add Enter 1.0g expanded graphites, 1.0g ammonium polyphosphate fully swells in the 1st network polymer and the 2nd network polymer, is warming up to 80 DEG C after mixing, the deionized water of 10ml is added, polymerisation is carried out under stirring, be prepared a kind of containing common The dynamic aggregation object of covalent cross-linking, side hydrogen bond group and boric acid estersil key.
The polymeric articles can be used for the vibration isolation of various motor vehicles, mechanical equipment, bridge, building, polymeric material For material when vibrated, the big energy that can dissipate plays damping, to effectively mitigate vibrations.
Embodiment 16
(1) with 1- methyl -2- (trimethoxy silane base) ethylmethyl acrylates and 1- (3- pyrrolidinyls) -2- third Alkene -1- ketone is monomer, and the molar ratio for controlling the two is 10:5,1- methyl -2- (trimethoxy silanes are made by free radical polymerization Base) ethylmethyl acrylate and 1- (3- pyrrolidinyls) -2- propylene -1- ketone copolymer (molecular weight is about 2800).
By above-mentioned copolymer 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, the deionized water of 6ml is added, polymerisation is carried out under stirring, one kind is prepared and contains side hydrogen bond The dynamic aggregation object of group and boric acid estersil key, as the 1st network polymer.
(2) side group carries the organopolysiloxane (molecular weight about 3000) and 2- mercaptoimidazoles, 1,9- of terminal olefin group Two mercaptan of nonyl is according to double bond and the molar ratio of sulfydryl 100:90:5 mixing, are added the photoinitiator benzoin dimethylether of 0.2wt% (DMPA), after stirring fully, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains being prepared a kind of containing side hydrogen bond group Organopolysiloxane.
The above-mentioned organopolysiloxane containing side hydrogen bond group and 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids The molar ratio 1 of ester Si-OR groups and B-OR groups:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, Polymerisation is carried out under stirring, and one kind is prepared and contains common covalent cross-linking, side hydrogen bond group and boric acid estersil key Dynamic aggregation object, as the 2nd network polymer.
(3) with methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and 3- allyls -2-Pyrrolidone, N, N '-methylene Bisacrylamide is monomer, and the molar ratio for controlling three is 10:5:1, methacrylic acid 3- (front threes are made by free radical polymerization Oxygroup silicon substrate) propyl ester and 3- allyls -2-Pyrrolidone, N, (molecular weight is about the copolymer of N '-methylene-bisacrylamides 5000)。
By above-mentioned copolymer and trimethylborate according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, fully It swells in the 1st network polymer and the 2nd network polymer, is warming up to 80 DEG C after mixing, the deionized water of 10ml is added, Polymerisation is carried out under stirring, and one kind is prepared and contains common covalent cross-linking, side hydrogen bond group and boric acid estersil key Dynamic aggregation object.
The polymeric articles can be applied to amortizing packaging material as energy-absorbing buffering material.
Embodiment 17
(1) 3- isocyanides acid propylene and 3- hydroxyl -1- propylene equimolar ratios are reacted, amino first of the both ends with vinyl is made Ester compound 17a.
Two mercaptan of 1,3- diphenyl propanes -2,2- and compound 17a, triallylamine are according to molar ratio 9:6:2 are mixed, It is placed on ultraviolet radioactive 8h in UV crosslinking instrument, a kind of polymer containing common covalent cross-linking is obtained, as the 1st network polymerization Object.
(2) PEG (molecular weight is about 12000) and 3.2g diphenyl of four arms of the ends 20g with trimethoxy silicon group Hydrogen borate ester mix, be warming up to 80 DEG C stir evenly after, the deionized water of 4ml is added, polymerisation is carried out under stirring, A kind of dynamic aggregation object containing boric acid estersil key is prepared, as the 2nd network polymer.
(3) N- allyls -1H- imidazoles -1- formamides, 1- (3- butene-1s-yl) -1H-1,2,4- triazoles in molar ratio 50: 30:60:1 mixing, adds the nano silicon dioxide of 25mg grain sizes 25nm, fully swells in the 1st network polymer and the 2nd network In polymer, the AIBN of 5mol% is added as initiator, is prepared by free radical polymerization a kind of containing common covalently friendship The dynamic aggregation object of connection, side hydrogen bond group and boric acid estersil key.
The polymeric articles can be applied to prepare magic toy and body-building material with stress response.
Embodiment 18
(1) four mercaptoacetate of pentaerythrite and diallyl adipate are mixed, the ratio of both control molal quantity is 1:2, it pours into the glass board mould for accompanying silica gel pad, is placed on ultraviolet radioactive 4h in UV crosslinking instrument, be made a kind of containing general The crosslinked polymer of valence in all, as the 1st network polymer.
(2) acetyl bromide of acrylic acid 2- amino-ethyls ester and equimolar equivalent is dissolved in dichloromethane, is catalyzed in triethylamine Under obtain the olefinic monomer 18a of amide bond.
Olefinic monomer 18a and tert-butyl acrylate in molar ratio 50:50 are sufficiently mixed, and add the AIBN of 5mol%, lead to It crosses free radical polymerization and one kind is prepared containing side hydrogen bond group dynamic aggregation object, as the 2nd network polymer.
Two acid esters of (3) two (3- morpholines ethoxysilylpropyl) (Z)-but-2-ene and ethoxy ylboronic acid according to mole Than 1:1 mixing, after being warming up to 80 DEG C, is added the deionized water of 10ml, polymerisation is carried out under stirring, is prepared one Non-crosslinked dynamic aggregation object of the kind containing boric acid estersil key.This noncrosslinking dynamic aggregation object is scattered in the 1st network polymer In the 2nd network polymer, a kind of dynamic aggregation containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key is obtained Object.
The polymeric articles can be used for preparing speed lockup's device of road and bridge.
Embodiment 19
(1) using Tert-butyl Methacrylate and trimethylol-propane trimethacrylate as monomer, rubbing for the two is controlled You are than being 50:1, the AIBN of 3mol% is added as initiator, Tert-butyl Methacrylate and three are made by free radical polymerization The copolymer (molecular weight is about 8000) of methylolpropane trimethacrylate, as the 1st network polymer.
(2) methacrylic dichlorosilane and two mercaptan of the 1,10- last of the ten Heavenly stems are according to molar ratio 2:1 mixing, using AIBN as initiator, Triethylamine is catalyst, and a kind of silicon-containing compound of silicone hydroxyl presoma is made by thiol-ene click-reactions.
By the silicon-containing compound of above-mentioned silicone hydroxyl presoma and boric acid according to molar ratio 3:4 are mixed, and are sufficiently stirred mixed It closes uniformly, 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 Dynamic aggregation object containing boric acid estersil key, as the 2nd network polymer.
(3) ethyl methacrylate and 2- (1H- imidazol-4 yls) ethylmethyl acrylates are 200 according to molar ratio:1, The AIBN of 3mol% is added as initiator, a kind of non-crosslinked supermolecule containing side hydrogen bond action is made by free radical polymerization Polymer (molecular weight is about 3000), by this non-cross-linked polymer for containing side hydrogen bond action swell in the 1st network polymer and In 2nd network polymer, a kind of dynamic aggregation object containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key is obtained.
The polymeric articles can be used for making antidetonation shear plate or pulsating stress carrying tool.
Embodiment 20
(1) it by 1,3,5- tri- (bromomethyl) benzene and sodium azide in DMF solution, stirs 2 days, it is (folded to be made 1,3,5- tri- N-methyl) benzene.
Adipic acid dipropargyl ester and (azido-methyl) benzene of 1,3,5- tri- are according to molar ratio 3:2 mixing, are added relative to list Catalyst CuBr (the PPh of body 0.1wt%3)3With three [(1- benzyls -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), stirring After being sufficiently mixed, 4h is reacted at 60 DEG C, a kind of polymer containing common covalent cross-linking is obtained, as the 1st network polymer.
(2) 3- chloropropyls dimethyl methoxy silane and boric acid are mixed according to equimolar ratio, are heated to 60 DEG C and are passed through stirring After being dissolved, a small amount of water reaction 3h is added, obtains a kind of boronic acid compounds containing boric acid estersil key.
By the polyethylene glycol (molecular weight about 5000) of silicone hydroxyl sealing end and the above-mentioned boronic acid compounds containing boric acid estersil key Molar ratio according to siloxanes and borate is about 1:1 mixing, is added a small amount of water, after being stirred evenly under the conditions of 80 DEG C, reaction A kind of non-crosslinked dynamic aggregation object containing boric acid estersil key is prepared, as the 2nd network polymer in 6h.
(3) two (2- mercaptoethyls) adipic acids, ester diallyl adipate and diallyl aminomethoxy antifebrin According to 51:50:1 mixing is added the talcum powder that 0.4g grain sizes are 50nm, the AIBN of 0.5wt% is added, by click-reaction system A kind of non-crosslinked supermolecule polymer containing side hydrogen bond action is obtained, this non-cross-linked polymer for containing side hydrogen bond action is swollen In the 1st network polymer and the 2nd network polymer, obtains one kind and containing common covalent cross-linking, side hydrogen bond group and boric acid silicon The dynamic aggregation object of ester bond.
The polymeric articles can be used for making damping shock absorber, be applied to various motor vehicles, mechanical equipment.
Embodiment 21
(1) Adipoyl Chloride and polypropylene oxide triol are about 1 according to the molar ratio of acyl chlorides and hydroxyl:1 reaction, obtains one kind Polymer containing common covalent cross-linking.
(2) by the poly dimethyl of methoxy group-phenyl hydrogen-containing siloxane (PHMS, molecular weight 10000) and a certain amount of Tert-butyl acrylate, the mixing of 2- (2- oxygen -1- imidazolidinyls) ethyl methacrylate, poly- diethyl containing hydrogen silicone oil in control reaction The molal quantity and tert-butyl acrylate, 2- (2- oxygen -1- imidazolidinyls) of middle active hydrogen atom (hydrogen atom being directly connected with Si) The ratio of double bond molal quantity is about 100 in ethyl methacrylate:99:1, addition reaction occurs using chloroplatinic acid as catalyst, The organopolysiloxane containing side hydrogen bond group is made.
5- Aminopentyls dimethyl methoxy silane and three-n-pentyl borates are mixed according to equimolar ratio, are heated to After 60 DEG C are dissolved by stirring, a small amount of water reaction 3h is added, obtains a kind of borate chemical combination containing boric acid estersil key Object.
The above-mentioned organopolysiloxane containing side hydrogen bond group and the above-mentioned boric acid ester compound containing boric acid estersil key are pressed According to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, is added dropwise to 20% a small amount of acetic acid aqueous solution, adds 5wt% Graphene powder, after being stirred evenly under the conditions of 50 DEG C, the reaction was continued 4h is prepared and a kind of containing side hydrogen bond group and boric acid This non-crosslinked dynamic aggregation object for containing side hydrogen bond group and boric acid estersil key is swollen by the non-crosslinked dynamic aggregation object of estersil key In the 1st network polymer, a kind of dynamic aggregation containing common covalent cross-linking, side hydrogen bond group and boric acid estersil key is obtained Object.
The polymeric articles show good viscoplasticity, have good isolation vibrations and stress buffer effect, can To be used as a kind of elastic buffer gasket.
Embodiment 22
(1) using brombutyl, mercapto hydroxypropyl methyl dimethoxysilane as raw material, using DMPA as photoinitiator, Under the conditions of ultraviolet light, polysiloxane grafted modified butyl rubber is made by mercaptan-alkene hydrocarbon click addition reactions.Siloxanes Graft modification butyl rubber, trimethylborate are 10 in mass ratio:1 with suitable di-n-butyltin dilaurate, antioxidant 168, antioxidant 1010 is added in small-sized internal mixer and is kneaded, and then takes out the material after being kneaded and is cooled down, and is placed in double Flakiness is suppressed in roller machine, is cooled down at room temperature, and cut-parts are dipped in 90 DEG C of bucks and carry out precrosslink, are subsequently placed in 80 DEG C 4h is placed in vacuum drying oven further to be reacted and dried, and little particle is broken into after the 1st network polymer is made.
(2) taking appropriate 1st network polymer little particle and brombutyl, (both control mass ratio is 1:5) it, is added Appropriate 1,6- ethanthiols, N- [(2- mercaptos ethyl) carbamyl] propionamides and benzoin dimethylether (DMPA), 2wt% hard charcoals Black, 2wt% titanium dioxides, 0.5wt% stearic acid, which are added in small-sized internal mixer, to be continued to be kneaded 20min, after then taking out mixing Material is cooled down, and is placed in twin-roll machine and is suppressed flakiness, is cooled down at room temperature, cut-parts.Film is placed in suitable mould In tool, ultraviolet light 10min is utilized at normal temperatures and pressures, is prepared a kind of containing common covalent cross-linking, side hydrogen bond group With the dynamic aggregation object of boric acid estersil key.
Obtained rubber-based dynamic aggregation object material has good resilience, can be as rubber buffer material application In sports goods field.
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 (24)

1. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that wherein at least include a covalent cross-linking net The degree of cross linking of network, common covalent cross-linking therein reaches its gel point or more；Simultaneously comprising the covalent inorganic boric acid estersil key of dynamic The supermolecule hydrogen bond action participated in side hydrogen bond group.
2. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the side hydrogen Key group contains hydrogen bond receptor or contains hydrogen bond donor or contain hydrogen bond receptor and hydrogen bond donor simultaneously.
3. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that wherein, institute The hydrogen bond receptor for stating side hydrogen bond group contains at least one of structure shown in the following general formula,
Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Selected from any appropriate Atom, group, segment, cluster；Wherein, R is selected from hydrogen atom, substitution atom, substituent group；
Wherein, the hydrogen bond donor of the side hydrogen bond group contains at least one of structure shown in the following general formula,
4. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that it contains Its composition has following any character：Gel, ordinary solid, elastomer, foam.
5. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that it was formed Recipe ingredient further includes following any or appoints several：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, crosslinking agent, curing agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation Agent, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickening Agent, levelling agent；
Wherein, the filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.
6. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object only there are one network, Include common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously in network, wherein common covalent cross-linking reaches More than its gel point, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include The side hydrogen bond action.
7. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking and dynamic covalent cross-linking, wherein the common covalent cross-linking reaches its gel Or more, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, does not contain the side hydrogen in side group and side chain Key group；Without covalently cross-linked in 2nd network, but polymer chain there are the side hydrogen bond group and participates in hydrogen bond crosslinks.
8. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein it is solidifying that the common covalent cross-linking reaches it More than glue point, the supermolecule hydrogen bond crosslinks are participated in realizing by side hydrogen bond group；Common covalent cross-linking is free of in 2nd network, But containing inorganic boric acid estersil key dynamic covalent cross-linking, the side hydrogen bond group is not contained.
9. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein it is solidifying that the common covalent cross-linking reaches it More than glue point, the supermolecule hydrogen bond crosslinks are participated in realizing by the side hydrogen bond group；Comprising common covalent in 2nd network Crosslinking and inorganic boric acid estersil key dynamic covalent cross-linking, wherein the common covalent cross-linking reaches its gel point or more, no Contain the side hydrogen bond group.
10. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalently to hand over Connection reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond is handed over Connection includes the side hydrogen bond action；Without covalently cross-linked in 2nd network, but polymer chain there are side hydrogen bond group and participates in Form hydrogen bond crosslinks.
11. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalently to hand over Connection reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond is handed over Connection includes the side hydrogen bond action；Contain common covalent cross-linking and inorganic boric acid estersil key dynamic covalent cross-linking in 2nd network, But it does not contain the side hydrogen bond group.
12. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalently to hand over Connection reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond is handed over Connection includes the side hydrogen bond action；It is handed over containing inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond in 2nd network Connection, the supermolecule hydrogen bond crosslinks are participated in realizing by the side hydrogen bond group.
13. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network includes common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalently to hand over Connection reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond is handed over Connection includes the side hydrogen bond action；2nd network is handed over comprising common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond simultaneously Connection, wherein common covalent cross-linking reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, The supermolecule hydrogen bond crosslinks include the side hydrogen bond action；But upper 1st and the 2nd network differs.
14. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by three networks It constitutes, common covalent cross-linking and inorganic boric acid estersil key dynamic covalent cross-linking is contained in the 1st network, but it does not contain the side hydrogen Key group；Without covalently cross-linked in 2nd network, but there are the side hydrogen bond groups on polymer chain, and form the side hydrogen The hydrogen bond crosslinks that key group participates in；3rd network is while being handed over comprising common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond Connection, wherein common covalent cross-linking reaches its gel point or more, and the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, The supermolecule hydrogen bond crosslinks include the side hydrogen bond action.
15. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by three networks It constitutes, inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen bond is contained in the 1st network Crosslinking is participated in realizing by the side hydrogen bond group, but does not contain common covalent cross-linking；Without covalently cross-linked in 2nd network, But there are the side hydrogen bond groups on polymer chain, and form the hydrogen bond crosslinks that the side hydrogen bond group participates in；3rd network is Include common covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks simultaneously, wherein common covalent cross-linking reaches its gel Or more, the dynamic covalent cross-linking is realized by inorganic boric acid estersil key, and the supermolecule hydrogen bond crosslinks include described Side hydrogen bond action.
16. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by three networks It constitutes, inorganic boric acid estersil key dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the supermolecule hydrogen bond is contained in the 1st network Crosslinking is participated in realizing by the side hydrogen bond group, but common covalent cross-linking is not present；2nd and the 3rd network is simultaneously comprising general Logical covalent cross-linking, dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, wherein common covalent cross-linking reaches its gel point or more, institute The dynamic covalent cross-linking stated is realized that the supermolecule hydrogen bond crosslinks include that the side hydrogen bond is made by inorganic boric acid estersil key With, but the 2nd is different with the 3rd network.
17. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by three networks It constitutes, the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen bond；2nd network is dynamic covalent cross-linking net Network is free of hydrogen bond crosslinks；3rd network is the hydrogen bond crosslinks network that the side hydrogen bond group participates in, without dynamic covalent cross-linking and Common covalent cross-linking.
18. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen bond；2nd network is the side hydrogen bond group The hydrogen bond crosslinks network of participation is free of dynamic covalent cross-linking and common covalent cross-linking；Contain the covalent inorganic boric acid estersil key of dynamic Non-crosslinked dynamic covalent polymer be scattered in above-mentioned two network.
19. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by two networks It constitutes, the 1st network is common covalent cross-linking network, does not contain dynamic covalent bond and hydrogen bond；2nd network is dynamic covalent cross-linking net Network is free of hydrogen bond crosslinks and common covalent cross-linking；Non-crosslinked supermolecule polymer containing side hydrogen bond action is scattered in above-mentioned two In a network.
20. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by a network It constitutes, cross-linked network is common covalent cross-linking network, without containing the covalently cross-linked and hydrogen bond crosslinks of dynamic；Contain the covalent nothing of dynamic The non-crosslinked dynamic covalent polymer of machine boric acid estersil key and the non-crosslinked dynamic supermolecule polymer containing side hydrogen bond are scattered in In above-mentioned network.
21. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by a network It constitutes, cross-linked network is common covalent cross-linking network, without containing the covalently cross-linked and hydrogen bond crosslinks of dynamic；Contain dynamic simultaneously altogether The non-crosslinked dynamic aggregation object of the inorganic boric acid estersil key of valence and side hydrogen bond is scattered in above-mentioned network.
22. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that the dynamic aggregation object is by a network It constitutes, cross-linked network is common covalent cross-linking network, and selectively contains the hydrogen bond crosslinks that the side hydrogen bond participates in；With dynamic The covalent inorganic crosslinked dynamic covalent polymer of boric acid estersil key is scattered in granular form in the network, wherein containing optional The side hydrogen bond participate in hydrogen bond crosslinks.
23. a kind of dynamic aggregation object with hybrid cross-linked structure according to any one of Claim 1-3,6 to 22, It is characterized in that, it is applied to following product：Damper, padded coaming, deadener, acoustic material, defense of resistance to impact material, Athletic protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, bulletproof glass folder Layer glue, toughness material, shape-memory material, sealing element, toy, force snesor.
24. a kind of method of energy-absorbing, which is characterized in that a kind of dynamic aggregation object with hybrid cross-linked structure of offer is as energy-absorbing Material simultaneously carries out energy-absorbing with it, and a covalent cross-linking network, common covalently friendship therein are included at least in the dynamic aggregation object The degree of cross linking of connection reaches its gel point or more；It is participated in simultaneously comprising the covalent inorganic boric acid estersil key of dynamic and side hydrogen bond group super Molecule hydrogen bond action.
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