CN108341954A - 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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CN108341954A
CN108341954A CN201710055916.0A CN201710055916A CN108341954A CN 108341954 A CN108341954 A CN 108341954A CN 201710055916 A CN201710055916 A CN 201710055916A CN 108341954 A CN108341954 A CN 108341954A
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dynamic
cross
network
linker
linked
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不公告发明人
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Xiamen iron cloth Mstar Technology Ltd.
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Weng Qiumei
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/05—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of dynamic aggregation objects with hybrid cross-linked structure, and it includes have common covalent cross-linking and dynamic covalently inorganic boric acid estersil key.Wherein, common covalent cross-linking imparts polymer with certain strength and stability, and covalently inorganic boric acid estersil key has dynamic reversibility to dynamic, possesses the functional characteristics such as excellent stimulating responsive, self-repairability, especially good energy-absorbing effect.The dynamic aggregation object can be widely used for making damping, buffering material, defense of resistance to impact material and shape memory 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 a kind of dynamic aggregation object with hybrid cross-linked structure and its Using.
Background technology
Traditional organosilicon material refers generally to the oligomeric or high polymer containing polysiloxane backbone.This one kind is based on polysiloxanes Traditional organosilicon material have many advantages, such as high-low temperature resistant, moisture-proof, insulation, corrosion-resistant, radiation hardness, ageing-resistant, but also tend to compare Relatively soft, mechanical property is bad, and if using the enhancings such as filler filling or traditional modification by copolymerization method, and often result in crosslinking Polymer is hard and crisp, its application is made to be restricted；And traditional organosilicon material lacks dynamic, and the performance of material is fixed Change.
Therefore, it is necessary to develop a kind of novel hybrid cross-linked dynamic aggregation object so that system can either keep certain soft Softness, 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, provides a kind of dynamic aggregation object with hybrid cross-linked structure, wherein at least wraps It is therein common covalently cross-linked to reach gel point or more containing a common covalent cross-linking network；Simultaneously comprising the covalent nothing of dynamic The supermolecule hydrogen bond action that skeleton hydrogen bond group existing for machine boric acid estersil key and selectivity participates in.Wherein, the dynamic is total Valence crosslinking is realized that supermolecule hydrogen bond crosslinks are realized by hydrogen bond existing for the selectivity by inorganic boric acid estersil key.Described Dynamic aggregation object also shows excellent dynamic reversibility while with certain mechanical strength and good toughness, and Reflect the functional characteristics such as dilatancy, self-repairability, tack.
The present invention is achieved by following technical solution：
A kind of dynamic aggregation object with hybrid cross-linked structure, wherein include a common covalent cross-linking network, it is described general Valence cross-linked network skeleton is polysiloxanes chain structure in all；It wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein institute It states any one B atom in the covalent inorganic boric acid estersil key of dynamic to connect with three-O-, and is at least partly based on at least two The linker of different Si atoms connection in the different B-O-Si keys of different B atoms is to contain in linker L, the linker L Carbon atom on dynamic covalent polymer main chain backbone.
A kind of dynamic aggregation object with hybrid cross-linked structure, wherein include a common covalent cross-linking network, it is described general Valence cross-linked network skeleton is siliceous heterochain structure in all, and is worked as in the siliceous heterochain containing the carbochain in cross-linked network skeleton Duan Shi, carbon atom therein are no less than 20；It wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein the dynamic Any one B atom is connect with three-O- in covalent inorganic boric acid estersil key, and at least partly different with being based on from least two The linker of the different Si atoms connection of the different B-O-Si keys of B atoms is in linker L, the linker L containing in dynamic Carbon atom on state covalent polymer main chain backbone.
A kind of dynamic aggregation object with hybrid cross-linked structure, wherein include at least two common covalent cross-linking networks, until A few common covalent cross-linking network skeleton is polysiloxane chain or siliceous heterochain structure；Wherein include that dynamic is covalent simultaneously Inorganic boric acid estersil key, wherein covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and It is at least partly connection from the linker of the different Si atoms connection in at least two different B-O-Si keys based on different B atoms Contain the carbon atom on dynamic covalent polymer main chain backbone in base L, the linker L.
(the first network structure) in a preferred embodiment of the present invention, it is described with hybrid cross-linked structure Dynamic aggregation object contains common covalent cross-linking and dynamic covalently inorganic boric acid estersil simultaneously only there are one cross-linked network in the network Key is crosslinked, and common covalent cross-linking reaches its gel point or more；Wherein, the common covalent cross-linking network skeleton is polysiloxane chain Structure；Covalently any one B atom connect to form three B-O-Si keys with three-O- the dynamic in inorganic boric acid estersil key, And the linker at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms is company It connects in base L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (second of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and wherein it is dispersed with the noncrosslinking dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, institute It is polysiloxanes chain structure to state common covalent cross-linking network skeleton；Covalent any one B in inorganic boric acid estersil key of the dynamic Atom is connect with three-O-, and at least partly former from the different Si in at least two different B-O-Si keys based on different B atoms The linker of son connection is former containing the carbon on dynamic covalent polymer main chain backbone in linker L, the linker L Son.
In another preferred embodiment of the present invention (the third network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and be wherein dispersed with the covalent inorganic crosslinked dynamic covalent polymer particle of borate key of dynamic；Wherein, described Common covalent cross-linking network skeleton is polysiloxanes chain structure；Covalently any one B is former in inorganic boric acid estersil key for the dynamic Son connect with three-O-, and at least partly from the different Si atoms in at least two different B-O-Si keys based on different B atoms The linker of connection is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the 4th kind of network structure), described has hybrid cross-linked structure Dynamic aggregation object contain there are two network；Common covalent cross-linking is contained only in 1st network；With inorganic boric acid estersil key in 2nd network The crosslinking of formation reaches its gel point or more, and without common covalent cross-linking more than gel point；Wherein, the common covalently friendship Connection network skeleton is polysiloxanes chain structure；The dynamic covalently any one B atom and three-O- in inorganic boric acid estersil key Connection, and the connection at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Base is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
(the 5th kind of network structure) in a preferred embodiment of the present invention, it is described dynamic with hybrid cross-linked structure State polymer contains common covalent cross-linking and dynamic covalently inorganic boric acid estersil key simultaneously only there are one cross-linked network in the network Crosslinking, common covalent cross-linking reach its gel point or more；Wherein, the common covalent cross-linking network skeleton is siliceous heterochain knot Structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20；Institute It states any one B atom in the covalent inorganic boric acid estersil key of dynamic to connect to form three B-O-Si keys with three-O-, and at least portion The linker from the different Si atoms connection in at least two different B-O-Si keys based on different B atoms is divided to be linker L, institute It states in linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the 6th kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and wherein it is dispersed with the noncrosslinking dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, institute It is siliceous heterochain structure to state common covalent cross-linking network skeleton, and is in cross-linked network skeleton when containing in the siliceous heterochain When carbochain section, carbon atom therein is no less than 20；Covalent any one the B atom and three in inorganic boric acid estersil key of the dynamic A-O- connections, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the 7th kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and be wherein dispersed with the covalent inorganic crosslinked dynamic covalent polymer particle of borate key of dynamic；Wherein, described Common covalent cross-linking network skeleton is siliceous heterochain structure, and is worked as in the siliceous heterochain containing the carbon in cross-linked network skeleton When segment, carbon atom therein is no less than 20；Covalent any one the B atom and three in inorganic boric acid estersil key of the dynamic A-O- connections, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the 8th kind of network structure), described has hybrid cross-linked structure Dynamic aggregation object contain there are two network；Common covalent cross-linking is contained only in 1st network；With inorganic boric acid estersil key in 2nd network The crosslinking of formation reaches its gel point or more, and without common covalent cross-linking more than gel point；Wherein, the common covalently friendship Connection network skeleton is siliceous heterochain structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, In carbon atom be no less than 20；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, And the linker at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms is company It connects in base L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.
(the 9th kind of network structure) in a preferred embodiment of the present invention, it is described with hybrid cross-linked structure Dynamic aggregation object contains there are two common covalent cross-linking network, contains common covalent cross-linking and dynamic in wherein at least one network simultaneously State covalently inorganic boric acid estersil key crosslinking；Wherein, at least one common covalent cross-linking network skeleton chains for polysiloxanes Structure or siliceous heterochain structure；Covalently any one B atom connect to form three the dynamic with three-O- in inorganic boric acid estersil key A B-O-Si keys, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker be in linker L, the linker L containing the carbon atom on the dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the tenth kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure common covalent cross-linking network containing there are two, and be wherein dispersed with noncrosslinking covalently inorganic containing dynamic The dynamic covalent polymer of boric acid ester bond；Wherein, at least one common covalent cross-linking network skeleton chains for polysiloxanes Structure or siliceous heterochain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and extremely Small part is linker from the linker of the different Si atoms connection in at least two different B-O-Si keys based on different B atoms Contain the carbon atom on dynamic covalent polymer main chain backbone in L, the linker L.
In another preferred embodiment of the present invention (a kind of the tenth network structure), described having is hybrid cross-linked The dynamic aggregation object of structure common covalent cross-linking network containing there are two, and be wherein dispersed with the covalent inorganic borate key of dynamic Crosslinked dynamic covalent polymer particle；Wherein, the common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous Heterochain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly with The linker of different Si atoms connection in at least two different B-O-Si keys based on different B atoms is linker L, the company It connects in base L containing the carbon atom on dynamic covalent polymer main chain backbone.
In another preferred embodiment of the present invention (the 12nd kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure network containing there are three, two of which is common covalent cross-linking network；Wherein in dynamic covalent cross-linking network The crosslinking formed with inorganic boric acid estersil key reaches its gel point or more, and without common covalent cross-linking more than gel point；Its In, at least one common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous heterochain structure；The dynamic is total Any one B atom is connect with three-O- in the inorganic boric acid estersil key of valence, and wherein at least partly from least two based on different The linker of different Si atoms connection in the different B-O-Si keys of B atoms is to contain to be in linker L, the linker L Carbon atom on dynamic covalent polymer main chain backbone.
In one embodiment of the present invention, the dynamic aggregation object with hybrid cross-linked structure contains one kind or one Kind or more hydrogen bond group, the hydrogen bond group is present in cross-linked polymer cross-linked network chain backbone or non-cross-linked polymer In main chain backbone, or exist simultaneously in cross-linked polymer cross-linked network chain backbone and non-cross-linked polymer main chain backbone.
In one embodiment of the present invention, the dynamic aggregation object with hybrid cross-linked structure is with following any Kind character：Ordinary solid, elastomer, gel, foam.
In one embodiment of the present invention, the dynamic aggregation object with hybrid cross-linked structure, which is characterized in that The raw material components for being used to prepare the dynamic aggregation object further include it is following any or appoint it is several can additive or usable object：Its His polymer, auxiliary agent, filler.Wherein, the other polymers are selected from following any or appoint several：Natural polymer chemical combination Object, synthetic resin, synthetic rubber, synthetic fibers；Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst draws Send out agent, antioxidant, light stabilizer, heat stabilizer, chain extender, toughener, coupling agent, crosslinking agent, curing agent, lubricant, demoulding 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 is selected from following any or appoints several：It is inorganic Non-metallic fillers, metal packing, organic filler.
In one embodiment of the present invention, the dynamic aggregation object with hybrid cross-linked structure is applied to following material Material or product：Damping shock absorber, speed lockup's device, antidetonation shear plate, pulsating stress carrying tool, padded coaming, shock resistance are anti- Protective material, athletic protective article, army and police's protective article, shape-memory material, stress sensitive material, magic toy, body-building material, Stress monitoring sensor, squeegee, bulletproof glass squeegee, blocks glue, casting glue, scratch resistant coatings, toughness material at binder Material, tough elastomer material, self-repairability coating, self-repairability plank, self-repairability binder, self-repairability sealing material, Self-repairability toughness material.
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, is commonly covalently handed in conventional silicone Dynamic covalently inorganic boric acid estersil key is introduced on the basis of networking network, the network of common covalent cross-linking is the dynamic aggregation object Balanced structure is provided, and covalently inorganic boric acid estersil key provides dynamic to the dynamic.It is described dynamic in different paradigmatic structures Covalently inorganic boric acid estersil key can both provide dynamic covalent cross-linking to state together with common covalent cross-linking in the same network, It can be individually formed dynamic covalent cross-linking network, the particle of dynamic crosslinking can also be individually formed, it can also be with noncrosslinking poly- Solvate form is dispersed in common covalent cross-linking network.In different polymer architectures, the covalent inorganic boric acid silicon of the dynamic Ester bond can play dynamic, the effects that playing energy-absorbing/damping/shock resistance, but different structure respectively has feature again, can be abundant Play respective advantage.For example, with common covalent cross-linking in the same cross-linked network when, the covalent nothing of dynamic under external force Machine boric acid estersil bond energy is broken in the form of " can sacrifice key " to the maximum extent, to a large amount of energy that dissipates, for crosslinking Polymer provides enough toughness so that cross-linked polymer is possessing the same of the intrinsic mechanical strength of cross-linked structure and stability When, also possess excellent tensile toughness and tear resistance.And when being only dispersed in cross-linked network with noncrosslinking polymer, energy It is enough that viscous loss is provided to the maximum extent.
(2) in a kind of dynamic aggregation object with hybrid cross-linked structure of the present invention, by increasing common covalent cross-linking The content of carbochain section and the number of common covalent cross-linking network, can step up the intensity of polymer, obtain power in network Learn the abundant dynamic aggregation object of performance level；By adjusting the dynamic covalent polymer containing the covalent inorganic boric acid estersil key of dynamic The topological structure and content of molecule can be prepared with the dynamic aggregation object for enriching different performance, polymeric acceptor can be made to show Go out stimulating responsive and dilatancy, polymer can make a response under the environmental stimulis such as external force, temperature, pH, illumination, change itself State meets the application demand of different occasions.
(3) also include skeleton existing for selectivity in a kind of dynamic aggregation object with hybrid cross-linked structure of the present invention Hydrogen bond group, the skeleton hydrogen bond group can form the supermolecule hydrogen bond with dynamic as the covalent inorganic boric acid silicon of dynamic The supplement of ester bond.Meanwhile dynamic, response between the supermolecule hydrogen bond based on dynamic and the covalent inorganic boric acid estersil key of dynamic The difference of property and intensity, can obtain fracture/dissociation under the dynamic change and response and stress of orthogonality/time sequence, from And the functions such as multiple response, energy absorption, selfreparing, shape memory are obtained to the maximum extent.This, which is the prior art, to carry It supplies.
(4) the covalent inorganic boric acid estersil key of dynamic in a kind of dynamic aggregation object with hybrid cross-linked structure of the present invention Dynamic response is strong, dynamic response mild condition, there is good thermal stability and high dynamic invertibity, can be without catalysis Agent, synthesis and dynamic reversibility without realizing dynamic aggregation object under conditions of high temperature, illumination or specific pH, prepare improving While efficiency, the limitation of use environment is also reduced, extends the application range of polymer.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific implementation mode
A kind of embodiment according to the present invention provides a kind of dynamic aggregation object with hybrid cross-linked structure, wherein wrapping Containing a common covalent cross-linking network, the common covalent cross-linking network skeleton is polysiloxanes chain structure；Wherein include simultaneously The covalent inorganic boric acid estersil key of dynamic, wherein the dynamic covalently any one B atom and three-in inorganic boric acid estersil key O- connections, and the company at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms It is the carbon atom contained in linker L, the linker L on dynamic covalent polymer main chain backbone to connect base.
Another embodiment according to the present invention provides a kind of dynamic aggregation object with hybrid cross-linked structure, wherein Including a common covalent cross-linking network, the common covalent cross-linking network skeleton is siliceous heterochain structure, and when described siliceous When in heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20；Wherein include dynamic simultaneously Covalent inorganic boric acid estersil key, wherein the dynamic covalently any one B atom and three-O- companies in inorganic boric acid estersil key The linker for connecing, and at least partly being connect with the different Si atoms of the different B-O-Si keys based on different B atoms from least two For linker L, the carbon atom on dynamic covalent polymer main chain backbone is contained in the linker L.
Another embodiment according to the present invention provides a kind of dynamic aggregation object with hybrid cross-linked structure, wherein Including at least two common covalent cross-linking networks, at least one common covalent cross-linking network skeleton is polysiloxane chain or contains Sila chain structure；It wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein the covalent inorganic boric acid estersil key of the dynamic In any one B atom connect with three-O-, and at least partly from at least two different B-O-Si keys based on different B atoms In different Si atoms connection linker be linker L, the linker L in containing be in dynamic covalent polymer main chain bone Carbon atom on frame.
Term " polymerization " used reaction is propagation process/effect of chain in the present invention, including reactant by polycondensation plus The process of product of the reaction formations such as poly-, the ring-opening polymerisation synthesis with higher molecular weight.Among these, reactant is typically The monomer of polymerizing power (can spontaneously be polymerize, or can be polymerize in initiator or outside plus under capable of acting on), The compounds such as oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds or two kinds with The product that upper reactant is polymerize is known as copolymer.It should be pointed out that " polymerization " in the present invention, packet The linear growth process of the chain containing reactant molecule includes the branched process of reactant molecule chain, including reactant molecule chain at Ring process also includes the cross-linking process of reactant molecule chain.
Term " crosslinking " used reaction in the present invention refers between reactant molecule and/or in reactant molecule by altogether Valence link is connected chemically to be formed with two dimension, three-dimensional cluster and the process for forming three-dimensional unlimited reticular pattern product in turn.It is being crosslinked In the process, polymer chain is general first constantly increases in two-dimensional/three-dimensional direction, and it (can be two dimension or three to gradually form cluster Dimension), developing deeply is three-dimensional infinite network.Unless stated otherwise, the present invention in cross-linked structure refer in particular to gel point or more (contain, under Three-dimensional infinite network structure together), non-crosslinked includes line style, branched, cyclic annular, two-dimentional cluster and gel point three-dimensional cluster knot below Structure isogel point structure below.
Heretofore described " gel point ", expression is reactant in cross-linking process, and viscosity is uprushed, and starts to coagulate Gelatinization phenomenon reaches reflecting point when a three-dimensional infinite network, also referred to as percolation threshold for the first time.Friendship more than gel point There is co-product three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer architecture；In solidifying Glue point cross-linking products below are only loose link structure, form three-dimensional infinite network structure, are only locally lying in A small amount of three-dimensional net structure, and it is not belonging to the cross-linked network that can constitute an entirety across entire polymer architecture.
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key (is generally not more than 100 DEG C) under typical temperature and (is generally less than 1 day) more difficult be broken in the usual time comprising But it is not limited only to common carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen Key, nitrogen-nitrogen key etc..
" the dynamic covalent bond " in embodiments of the present invention, that refer to is only inorganic boric acid estersil key (B-O- Si).In the present invention, it is preferred to which any one B atom for forming inorganic boric acid estersil key forms three B-O-Si keys.
Heretofore described " common covalent cross-linking network " refers to only carrying out crosslinked system with common covalent bond； Or when dynamic covalent bond all in system all disconnects, and only remains common covalently cross-linked, still with more than gel point poly- Polymeric network.Heretofore described " dynamic covalent cross-linking network " is referred to when the covalent nothing of dynamic in covalent cross-linking network When machine boric acid estersil key section or all dissociation, following any or several lists are resolved into original crosslinked polymer network dissociation Member：The secondary units such as monomer, polymer chain segment, polymer cluster, more than gel point polymer beads.
In the present invention, " skeleton " refers to structure on the chain length direction of polymer chain.It is described for cross-linked polymer " main chain ", refer to the arbitrary segment being present in cross-linked network skeleton, i.e., connected in cross-linked network between adjacent crosslinking points Skeletal chain comprising main chain and crosslinking on unlimited three-dimensional network skeleton link；Wherein, the crosslinking link between polymer chain can Think an atom, a singly-bound, a group, a segment, a cluster etc..For the polymer of non-crosslinking structure, " main chain " refers to the most chain of chain link if not otherwise indicated.Wherein, " side chain ", refers to same polymer Main chain is connected and is distributed in the chain structure of main chain side；Wherein, " branch "/" bifurcated chain " can be that side chain can also It is the chain structure that other come out from arbitrary chain bifurcated.Wherein, " side group ", refer to the arbitrary chain of same polymer be connected and It is distributed in the chemical group of chain side.Wherein, " end group " refers to that the arbitrary chain of same polymer is connected and is located at last-in-chain(LIC) The chemical group at end.If not otherwise indicated, the molecular weight that side group refers in particular to be connected to polymer chain skeleton side is no more than 1000Da Group and subunit group therein.When the molecular weight of side chain, bifurcated chain is no more than 1000Da, itself and group thereon regard For side group.For the sake of simplicity, when the molecular weight of side chain, bifurcated chain is more than 1000Da, if not otherwise indicated, then it is collectively referred to as side Chain.Above-mentioned " side chain ", " side group " can have multilevel hierarchy namely side chain/side group that can continue to carry side chain/side group, side Side chain/side group of chain/side group can continue have side chain/side group.In the present invention, for hyperbranched and dendroid chain and its relevant The polymer segment of chain structure, outermost can be considered as side chain, and rest part can be considered as main chain.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention Can include to be selected from the option of the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
In embodiments of the present invention, covalently inorganic boric acid estersil key can reside in dynamic aggregation object to the dynamic On main chain chain, it can reside in the side group and/or side chain of main chain and its side group and/or side chain of next stage and/or lower multistage On, it can also be in the side group of polymer chain and/or end group.Under suitable conditions, in dynamic aggregation object any position it is dynamic State covalent bond can participate in dynamic reversible exchange.The polymer containing the inorganic boric acid estersil key is that dynamic is covalent on chain Polymer.
In embodiments of the present invention, the polysiloxane chain refers on main chain only containing silicon atom and oxygen atom Compound or polymer；The siliceous heterochain refers on main chain in addition to containing silicon atom, also at least contains a kind of deoxygenation The compound or polymer of other atoms other than atom, wherein other described atoms are at least divalent, include as an example But be not limited to C, N, P, S, Se, Ni, Co, Pt, Ru, Ti, Al, Ir etc..As an example, siliceous heterochain includes but not limited to poly- silicon nitrogen Alkane and its copolymer, polymethylene silane and its copolymer, polyhenylene silane and its copolymer, polysilane copolymers, poly- silica Alkyl copolymer and polymer etc. obtained from the siliceous or not siliceous prepolymer of silane or other siliceous cross-linking agents. In embodiments of the present invention, when in the siliceous heterochain of cross-linked network containing the carbochain section in cross-linked network skeleton, wherein Carbon atom be no less than 20, therefore be conducive to improve the mechanical strength of common covalent cross-linking network, and facilitate adjusting hardness.
In embodiments of the present invention, in addition to the linker L, partly from least two based on different B atoms not Linker with the different Si atoms connection in B-O-Si keys can also be other any appropriate linkers；Except at least two Outside the linker of different Si atoms connection in different B-O-Si keys based on different B atoms, there can also be other linkers, make For citing comprising but be not limited to：It is connected from the different Si atoms in at least two different B-O-Si keys based on same B atoms Linker, from the linker etc. of the same Si atoms connection in at least two different B-O-Si keys based on different B atoms.Institute State linker L and other linkers be at least divalent, can be low molecular weight (average molecular weight is less than or equal to 1000Da, under Together) or the linker of high molecular weight (average molecular weight is more than 1000Da, similarly hereinafter), preferably molecular weight are more than 1000 macromolecule Linker.It is preferred that the amount of carbon atom contained in linker L is not less than 20, and it is directly former with the Si of B-O-Si by carbon atom Son is connected, and can not only obtain the dynamic of B-O-Si keys, but also can maximally utilise the performance of carbon atoms linker L. Other described linkers can be any appropriate linker, can contain carbon atom or not contain carbon atom.Linker L and Other linkers can have any appropriate topological structure, and including but not limited to line style, ring-type (include but not limited to monocycle, more Ring, nested rings, bridged ring), branched (including but not limited to star-like, H-type, combed, dendroid, hyperbranched), two and three dimensions cluster, And the random suitable combination of the above structure, even there is the particle (including fiber and sheet-like particle) of common covalent cross-linking. The linker L and other linkers can be homopolymers, can also be copolymer；Can be rigid connection base can also be soft Property linker, rigid connection base can assign the better rigidity of dynamic covalent polymer and modulus, and flexible linking group can assign dynamic The better flexibility of covalent copolymer, extensibility and plasticity.The linker L is not preferably low containing continuous amount of carbon atom In the alkyl of 20 alkyl segment, polyolefin-based, polyurethane, polyureas base, polysulfide for amine ester group, polyacrylic acid ester group；Other Linker is preferably polysiloxane group, poly- silithiane base；But the present invention is not limited only to this.According to the embodiment of the present invention, one More than one different linkers can be contained in a dynamic covalent polymer.Other linkers can be low molecular weight or height The linker of molecular weight, preferably molecular weight are more than 1000 macromolecule linker.The content that linker L accounts for all linkers does not have There is special limitation, preferably in 10-90mol%, more preferably in 30-70mol%, most preferably in 40-60mol%.
Can include one or more polymer molecule, and above-mentioned each implementation in the dynamic aggregation object of the present invention All included at least in dynamic aggregation object in mode common covalent cross-linking network namely at least one network it is common It is covalently cross-linked to reach its gel point or more.Covalently inorganic boric acid estersil key can be in common covalently cross-linked net for the dynamic Crosslinking is constituted in network together, dynamic covalent cross-linking network can also be individually formed, it can also be in non-crosslinked chain.Because at least wrapping Network containing a common covalent cross-linking, so even if in the case where all dynamic keys will be completely dissociated, polymerization of the invention Objects system can also keep balanced structure, and basic shape can also be kept not occur completely melting and dissolving.It keeps Balanced structure means can be with self-supporting, to many using most important of polymer, such as sealing ring, tire etc..When dynamic When polymer is made of two or more cross-linked networks, it can be made of two or more cross-linked networks being mutually blended, It can be made of two or more mutually interspersed cross-linked networks, it can also be by the mutually interspersed cross-linked network in two or more parts Network is constituted, but the present invention is not limited only to this；Wherein, two or more cross-linked networks may be the same or different.When there are two When a and its above common covalent cross-linking network, the mechanical strength of the dynamic aggregation object significantly improves.Crosslinked dynamic is covalent Polymer can form interpenetrating, partial interpenetrating structure with the common covalent cross-linking network, can also be with crosslinked particle etc. Form is dispersed in common covalent cross-linking network.When dynamic aggregation object is simultaneously comprising crosslinking and when non-crosslinked ingredient, it is non-crosslinked at It point can not also be evenly dispersed in cross-linked network with homogeneous blend/be interspersed in cross-linked network, it can also be noncrosslinking The forms such as particle are dispersed in common covalent cross-linking network；Can there be blending or incompatibly total between multiple non-crosslinked ingredients It is mixed.The present invention is not limited only to this, and those skilled in the art can be given with logic according to the present invention and train of thought and reasonably be realized.
(the first network structure) in a preferred embodiment of the present invention, it is described with hybrid cross-linked structure Dynamic aggregation object contains common covalent cross-linking and dynamic covalently inorganic boric acid estersil simultaneously only there are one cross-linked network in the network Key is crosslinked, and common covalent cross-linking reaches its gel point or more；Wherein, the common covalent cross-linking network skeleton is polysiloxane chain Structure；Covalently any one B atom connect to form three B-O-Si keys with three-O- the dynamic in inorganic boric acid estersil key, And the linker at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms is company It connects in base L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.In the network structure, structure Simply, it can keep balanced structure, inorganic boric acid estersil key that can provide common covalent cross-linking supplement by covalent cross-linking, and Covalent dynamic is provided.
In another preferred embodiment of the present invention (second of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and wherein it is dispersed with the noncrosslinking dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, institute It is polysiloxanes chain structure to state common covalent cross-linking network skeleton；Covalent any one B in inorganic boric acid estersil key of the dynamic Atom is connect with three-O-, and at least partly former from the different Si in at least two different B-O-Si keys based on different B atoms The linker of son connection is former containing the carbon on dynamic covalent polymer main chain backbone in linker L, the linker L Son.In the network structure, balanced structure is provided with common covalent cross-linking network, and disperses non-crosslinked dynamic therein and covalently polymerize Object provides dynamic, especially stress/strain response, is conducive to obtain higher viscous loss.
In another preferred embodiment of the present invention (the third network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and be wherein dispersed with the covalent inorganic crosslinked dynamic covalent polymer particle of borate key of dynamic；Wherein, described Common covalent cross-linking network skeleton is polysiloxanes chain structure；Covalently any one B is former in inorganic boric acid estersil key for the dynamic Son connect with three-O-, and at least partly from the different Si atoms in at least two different B-O-Si keys based on different B atoms The linker of connection is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone. In the network structure, balanced structure is provided with common covalent cross-linking network, and disperses crosslinking dynamic covalent polymer therein Grain provides dynamic, and local viscosity can be obtained when stress/strain responds and intensity increases.
In another preferred embodiment of the present invention (the 4th kind of network structure), described has hybrid cross-linked structure Dynamic aggregation object contain there are two network；Common covalent cross-linking is contained only in 1st network；With inorganic boric acid estersil key in 2nd network The crosslinking of formation reaches its gel point or more, and without common covalent cross-linking more than gel point；Wherein, the common covalently friendship Connection network skeleton is polysiloxanes chain structure；The dynamic covalently any one B atom and three-O- in inorganic boric acid estersil key Connection, and the connection at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Base is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.The network structure In, balanced structure is kept by the covalent cross-linking in the 1st network, the inorganic boric acid estersil key in the 2nd network provides covalently dynamic Property.
(the 5th kind of network structure) in a preferred embodiment of the present invention, it is described dynamic with hybrid cross-linked structure State polymer contains common covalent cross-linking and dynamic covalently inorganic boric acid estersil key simultaneously only there are one cross-linked network in the network Crosslinking, common covalent cross-linking reach its gel point or more；Wherein, the common covalent cross-linking network skeleton is siliceous heterochain knot Structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20；Institute It states any one B atom in the covalent inorganic boric acid estersil key of dynamic to connect to form three B-O-Si keys with three-O-, and at least portion The linker from the different Si atoms connection in at least two different B-O-Si keys based on different B atoms is divided to be linker L, institute It states in linker L containing the carbon atom on dynamic covalent polymer main chain backbone.It is simple in structure in the network structure, lead to Balanced structure can be kept by crossing covalent cross-linking, and inorganic boric acid estersil key can provide common covalent cross-linking supplement, and provide altogether Valence dynamic.
In another preferred embodiment of the present invention (the 6th kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and wherein it is dispersed with the noncrosslinking dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, institute It is siliceous heterochain structure to state common covalent cross-linking network skeleton, and is in cross-linked network skeleton when containing in the siliceous heterochain When carbochain section, carbon atom therein is no less than 20；Covalent any one the B atom and three in inorganic boric acid estersil key of the dynamic A-O- connections, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.The network In structure, balanced structure is provided with common covalent cross-linking network, and it is dynamic to disperse non-crosslinked dynamic covalent polymer offer therein State property, especially stress/strain response are conducive to obtain higher viscous loss.
In another preferred embodiment of the present invention (the 7th kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure is only there are one network, which only has common covalent cross-linking, and common covalent cross-linking therein reaches gel Or more, and be wherein dispersed with the covalent inorganic crosslinked dynamic covalent polymer particle of borate key of dynamic；Wherein, described Common covalent cross-linking network skeleton is siliceous heterochain structure, and is worked as in the siliceous heterochain containing the carbon in cross-linked network skeleton When segment, carbon atom therein is no less than 20；Covalent any one the B atom and three in inorganic boric acid estersil key of the dynamic A-O- connections, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker is in linker L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.The network In structure, balanced structure is provided with common covalent cross-linking network, and disperses crosslinking dynamic covalent polymer particle therein and provides Dynamic, local viscosity can be obtained when stress/strain responds and intensity increases.
In another preferred embodiment of the present invention (the 8th kind of network structure), described has hybrid cross-linked structure Dynamic aggregation object contain there are two network；Common covalent cross-linking is contained only in 1st network；With inorganic boric acid estersil key in 2nd network The crosslinking of formation reaches its gel point or more, and without common covalent cross-linking more than gel point；Wherein, the common covalently friendship Connection network skeleton is siliceous heterochain structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, In carbon atom be no less than 20；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, And the linker at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms is company It connects in base L, the linker L containing the carbon atom on dynamic covalent polymer main chain backbone.In the network structure, pass through Covalent cross-linking in 1st network keeps balanced structure, and the inorganic boric acid estersil key in the 2nd network provides covalent dynamic.
(the 9th kind of network structure) in a preferred embodiment of the present invention, it is described with hybrid cross-linked structure Dynamic aggregation object contains there are two common covalent cross-linking network, contains common covalent cross-linking and dynamic in wherein at least one network simultaneously State covalently inorganic boric acid estersil key crosslinking；Wherein, at least one common covalent cross-linking network skeleton chains for polysiloxanes Structure or siliceous heterochain structure；Covalently any one B atom connect to form three the dynamic with three-O- in inorganic boric acid estersil key A B-O-Si keys, and at least partly connected from the different Si atoms in at least two different B-O-Si keys based on different B atoms Linker be in linker L, the linker L containing the carbon atom on the dynamic covalent polymer main chain backbone.The net In network structure, there are two common covalent cross-linking networks for tool, and better power can be obtained by the combination of common covalent cross-linking network Intensity is learned, inorganic boric acid estersil key can provide supplement to common covalent cross-linking, and provide covalent dynamic.
In another preferred embodiment of the present invention (the tenth kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure common covalent cross-linking network containing there are two, and be wherein dispersed with noncrosslinking covalently inorganic containing dynamic The dynamic covalent polymer of boric acid ester bond；Wherein, at least one common covalent cross-linking network skeleton chains for polysiloxanes Structure or siliceous heterochain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and extremely Small part is linker from the linker of the different Si atoms connection in at least two different B-O-Si keys based on different B atoms Contain the carbon atom on dynamic covalent polymer main chain backbone in L, the linker L.In the network structure, there are two tools Common covalent cross-linking network can obtain better mechanical strength by the combination of common covalent cross-linking network, and disperse wherein Non-crosslinked dynamic covalent polymer dynamic, especially stress/strain response are provided, be conducive to obtain higher viscosity damage Consumption.
In another preferred embodiment of the present invention (a kind of the tenth network structure), described having is hybrid cross-linked The dynamic aggregation object of structure common covalent cross-linking network containing there are two, and be wherein dispersed with the covalent inorganic borate key of dynamic Crosslinked dynamic covalent polymer particle；Wherein, the common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous Heterochain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly with The linker of different Si atoms connection in at least two different B-O-Si keys based on different B atoms is linker L, the company It connects in base L containing the carbon atom on dynamic covalent polymer main chain backbone.In the network structure, there are two common covalent for tool Cross-linked network can obtain better mechanical strength by the combination of common covalent cross-linking network, and it is dynamic to disperse crosslinking therein State covalent polymer particle provides dynamic, and local viscosity can be obtained when stress/strain responds and intensity increases.
In another preferred embodiment of the present invention (the 12nd kind of network structure), described has hybrid cross-linked knot The dynamic aggregation object of structure network containing there are three, two of which is common covalent cross-linking network；Wherein in dynamic covalent cross-linking network The crosslinking formed with inorganic boric acid estersil key reaches its gel point or more, and without common covalent cross-linking more than gel point；Its In, at least one common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous heterochain structure；The dynamic is total Any one B atom is connect with three-O- in the inorganic boric acid estersil key of valence, and wherein at least partly from least two based on different The linker of different Si atoms connection in the different B-O-Si keys of B atoms is to contain to be in linker L, the linker L Carbon atom on dynamic covalent polymer main chain backbone.In the network structure, pass through being total in two common covalent cross-linking networks Valence crosslinking keeps balanced structure and provides strong mechanical property, and the inorganic boric acid estersil key in dynamic covalent cross-linking network provides altogether Valence dynamic.
In the present invention, can also have other diversified embodiments, can contain first there are three or more net Network, and the degree of cross linking of heterogeneous networks, topological structure, chemical constitution etc. can be identical or different.Those skilled in the art can With logic according to the present invention and train of thought, rationally and effectively realize.
In embodiments of the present invention, the dynamic aggregation object also optionally contains one or more kinds of presence Hydrogen bond group (hereinafter referred to as " bone in cross-linked polymer cross-linked network chain backbone and/or non-cross-linked polymer main chain backbone Frame hydrogen bond group "), form skeleton supermolecule hydrogen bond action.The supermolecule hydrogen bond action can be used as supermolecule polymerization and/ Or crosslinking and/or chain in ring formation exist namely hydrogen bond can only play connect two or more chain segment units play Increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond and only play the crosslinking of interchain supermolecule, or only plays chain Two or more arbitrary combination in interior ring formation or three of the above.
In embodiments of the present invention, the number of teeth of skeleton hydrogen bond is not limited.Since the number of teeth of hydrogen bond is more, collaboration Effect is bigger, and the intensity of hydrogen bond is bigger, if the more intensity of the number of teeth of hydrogen bond are big, the dynamic of hydrogen bond action is just weak, makees Be conducive to play when being crosslinked for supermolecule and promote dynamic aggregation object to keep balanced structure and improve mechanical property (modulus and intensity) Effect.If it is low that the number of teeth of hydrogen bond lacks intensity, the dynamic of hydrogen bond action, can be with dynamically covalent boric acid estersil key one with regard to strong It rises and dynamic property, such as self-repairability, energy absorption characteristics is provided.
In embodiments of the present invention, skeleton hydrogen bond group has structure diversity, including but not limited to hydrogen bond donor With the quantity etc. of the hydrogen bond group connected on receptor number, group size, polymer chain, intensity, dynamic, response can be obtained Property, crosslink density adjustable hydrogen bond crosslinks on a large scale, while by the regulation and control pair linked with polymer chain, hydrogen bond can be controlled The glass transition temperature etc. of dynamic, cross-linked polymer, and then effectively regulate and control every dynamic property of dynamic aggregation object.
In embodiments of the present invention, the skeleton hydrogen bond group that the polymer carries can only contain hydrogen bond donor Hydrogen bond group, can also be the only hydrogen bond group containing hydrogen bond receptor, can also be contain simultaneously hydrogen bond donor and hydrogen bond by The hydrogen bond group of body.When individual hydrogen bond group by only containing hydrogen bond donor or hydrogen bond receptor in the form of in the presence of, while it is necessary Containing must there are other additives to contain corresponding hydrogen bond receptor or hydrogen in corresponding hydrogen bond receptor or hydrogen-bond donor or system Key donor, to form hydrogen bond.The hydrogen bond donor is exactly hydrogen atom (H), the hydrogen bond receptor be exactly receive hydrogen atom electricity it is negative Property atom, including but not limited to oxygen atom (O), nitrogen-atoms (N), sulphur atom (S), fluorine atom (F) etc..Such atom can be in base Exist with suitable valence state in group.In embodiments of the present invention, the supermolecule hydrogen bond action can be by any appropriate Hydrogen bond group between existing noncovalent interaction generate.In order to be effectively formed hydrogen bond, preferably contains hydrogen bond simultaneously and supply The hydrogen bond group of body and hydrogen bond receptor, such as amide groups, carbamate groups, urea groups, thiocarbamate base, imidazoles, nitrogen azoles And the derivative etc. of the above group, at least one of further preferably following constituent：
In embodiments of the present invention, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this)：
In embodiments of the present invention, the inorganic boric acid estersil key (B-O-Si) preferably by inorganic compounds of boron and Silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma reacts.
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 heretofore described silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma, refer to compound end group and/ Or side group contains silicone hydroxyl and/or silicone hydroxyl presoma group.In the silicon-containing compound itself containing linker L/ other Linker passes through other linkers of generation linker L/ after suitably chemically reacting.Since linker L skeletons contain carbon atom, Especially linker containing carbon polymer can obtain the various dynamic aggregation object skeleton of structure-rich, performance, especially skeleton carbon Presence can facilitate and obtain higher dynamic aggregation object mechanical property, impressionability etc..
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), silicon atom preferably therein is at least connected with a carbon atom by silicon-carbon bonds, and at least One organic group is keyed to by the silicon-carbon on silicon atom.In the present invention, a hydroxyl (- OH) in silicone hydroxyl is i.e. For 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-X) that the group of hydroxyl is formed, wherein X 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 (- X) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is a functional group.
In order to illustrate the heretofore described linker containing carbon atoms silicon-containing compound and its produce described contain The silicon-containing compound of linker, the silicon-containing compound of the present invention for producing the L containing linker can be exemplified below, but The present invention is not limited only to this：
Wherein m, n, the quantity that x, y, z is repetitive unit, can be fixed value or average value.
For polysiloxanes, silicone hydroxyl can be in the end of polymer chain, can also be in the side group of polymer chain；Equally Ground, for the organopolysiloxane of siliceous hydroxyl groups precursors, silicone hydroxyl presoma can be in the end of polymer chain, can also be The side group of polymer chain.For small molecule siloxanes, silicone hydroxyl/silicone hydroxyl presoma equally can be end group or side group.
In the present invention, described (poly-) silicone compounds containing silicone hydroxyl and/or silicone hydroxyl presoma can illustrate such as Under, but the present invention is not limited only to this：
Wherein m, n are the quantity of repetitive unit, can be fixed value or average value.
In the present invention, any appropriate inorganic compounds of boron may be used and contain silicone hydroxyl and/or silicone hydroxyl presoma Compound combination generate dynamic covalently inorganic boric acid estersil key, it is preferred to use inorganic boric acid and the macromolecular containing silicone hydroxyl Close the macromolecular compound, inorganic borate (salt) and the macromolecular containing silicone hydroxyl of object, inorganic boric acid and siliceous hydroxyl groups precursors Compound forms inorganic boric acid estersil key, more preferably uses inorganic boric acid and macromolecular compound, Inorganic Boron containing silicone hydroxyl Acid esters forms inorganic boric acid estersil key with the macromolecular compound containing silicone hydroxyl, more preferably uses inorganic borate and siliceous hydroxyl The macromolecular compound of base forms inorganic boric acid estersil key.
In embodiments of the present invention, can covalently be gathered to obtain the dynamic by generating inorganic boric acid estersil key Object is closed, can also first preparing the compound containing the inorganic boric acid estersil key, polymerized/cross-linked is total to generate the dynamic again Valence 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 Conjunction process generates the inorganic boric acid estersil key and can be easy to cause to form bifurcated and can be crosslinked in turn.
In the present invention, dynamic covalent polymer itself can have any appropriate topological structure, including but not limited to Line style, ring-type (include but not limited to monocycle, polycyclic, nested rings, bridged ring), it is branched (including but not limited to starlike, H-type, pectination, It is dendroid, hyperbranched), two-dimensional/three-dimensional cluster, three-dimensional infinite network cross-linked structure and combinations of the above form.Polymer chain With side group, side chain, branch, and side group, side chain, branch can continue, with side group, side chain, branch, can also have Multilevel hierarchy.
In embodiments of the present invention, any appropriate reaction may be used in the generation or introducing of skeleton hydrogen bond group, packet It includes but is not limited only to Types Below：Isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, succinimide ester groups and ammonia Reaction between base, hydroxyl, sulfydryl, active ester and amino, hydroxyl, sulfydryl react, acyl halide group and amino, hydroxyl, sulfydryl Reaction, anhydride group and amino, hydroxyl, sulfydryl react, and epoxy and amino, hydroxyl, sulfydryl react, urea-amine it is anti- It answers, amidation process, free radical acrylate reaction, double bond radical reaction, double bond cyclization, nitrine-alkynes click-reaction, Sulfydryl-double bond/alkynes click-reaction, tetrazine-norbornene reaction, silicone hydroxyl condensation reaction；Preferred isocyanate and amino, hydroxyl The reaction of base, sulfydryl, the reaction of urea-amine, active ester and amino, hydroxyl, sulfydryl react；More preferable isocyanates and ammonia The reaction of base, hydroxyl, sulfydryl.The generation or introducing of hydrogen bond group can there are one or more reaction type, reaction means, shape At supermolecule crosslinking can there are one or more type, structure.
In embodiments of the present invention, the form of the dynamic aggregation object or its composition can be ordinary solid, bullet Property body, (including the swelling of hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid is solidifying for gel Glue), foam etc..Compared with ordinary solid, gel is more soft, and foam density is lower more light, while soft bubble also has both There is the characteristic of soft comfortable, both there is strong energy absorption capacity.Wherein, the small-molecular-weight ingredient contained in ordinary solid and foam contains Amount is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.
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 dynamic crosslinking acquisition, can also be in dynamic aggregation object system Sweller is recycled to carry out swelling acquisition after the completion of standby.Certainly, the present invention not only limit and this, those skilled in the art can basis The logic and train of thought of the present invention, 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 four method：(1) inert gas blown method, i.e., inert gas under pressurized condition It is pressed into molten polymer or pasty material, then decompression heating, makes the gas expansion of dissolving and foam；(2) low boiling point is utilized Liquid evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, keep liquid molten Enter in polymer beads, then heat and soften polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching uses liquid Body medium, which immerses in polymer, dissolves the solid matter added in advance, makes to occur a large amount of holes in polymer and be in foaming Shape, such as by solable matter salt, 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, i.e., in being added in the plastic Become obturator-type foamed plastics through solidification after empty microballoon；Wherein, preferably by dissolving in inert gas and low boiling in the polymer The method of point liquid foams.Using physical blowing method, have operation Poisoning smaller, foaming raw material cost is relatively low, foaming The advantages that agent noresidue body.Further, it is also possible to be prepared using freeze-drying.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, 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.
In the present invention, it is used to prepare the composition of raw materials component of dynamic aggregation object, except the inorganic compounds of boron and siliceous Further include the other polymers that can be added/use, auxiliary agent, filler except compound, these can add/and it can be to be total to using object Form that is mixed, participating in chemical reaction is with the reaction product of inorganic compounds of boron and silicon-containing compound collectively as with hybrid cross-linked The dynamic aggregation composition formula component of structure, or play the role of improvement processing performance in the preparation process of dynamic aggregation object.
The other polymers can play in system and improve material property, assign material new capability, improve material Material using with economic benefit, have the function that material comprehensively utilize.The other polymers, can be selected from natural polymer Close object, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to the character of polymer added and possessed molecule Amount does not limit, and can be oligomer or high polymer, according to the difference of polymeric species, Ke Yiwei according to the difference of molecular weight Homopolymer or copolymer, in the specific use process should be according to the performance of target material and the needs of actual fabrication process And it is selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound：Natural rubber, chitosan, chitin, native protein etc..
When the other polymers are selected from synthetic resin, it can be selected from following any or appoint several synthetic resin： Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), makrolon, Dimethyl silicone polymer, polyethylene, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane Copolymer, polyimides, polymethyl acrylate, polymethyl methacrylate, polymethacrylonitrile, polyphenylene oxide, polypropylene, polyphenyl Thioether, polyphenylsulfone, polystyrene, high impact polystyrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, Ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, AAS acrylonitrile acryloid styrene, acrylic nitrile-butadiene Diene-styrene copolymer, vinyl chloride vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, urea Urea formaldehyde, unsaturated polyester (UP) etc..
When the other polymers are selected from synthetic rubber, it can be selected from following any or appoint several synthetic rubber： Isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorubber, Lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc..
When the other polymers are selected from synthetic fibers, it can be selected from following any or appoint several synthetic fibers： Viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane fiber, polypropylene Nitrile fiber, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..
Wherein, the preferred natural rubber of the other polymers, polyethylene, polypropylene, ethylene-vinyl acetate c It is object, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polymethyl methacrylate, epoxy resin, phenolic resin, different Penta rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, polyurethane rubber Glue, thermoplastic elastomer (TPE).
The auxiliary agent can improve material preparation process, improve product quality and yield, reduce product cost or Assign product certain distinctive application performance.The addible auxiliary agent is selected from following any or several auxiliary agents：Synthesis Auxiliary agent, including catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer；Improve mechanical property Auxiliary agent, including chain extender, toughener, coupling agent, crosslinking agent, curing agent；Improve the auxiliary agent of processing performance, including lubricant, de- Mould agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change the auxiliary agent of surface property, packet Include antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；Fire retardantization with Press down 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 reaction between some active groups needs catalyst, such as：(1) polyurethane synthesizes Use catalyst：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- dimethylaminos-second Oxygroup) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyls) two are different Propanolamine, N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyl cyclohexyl amines, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethylethanolamines, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls caproic acid, N, N- dimethyl benzylamines, N, N- Dimethyl cetylamine etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, two bay of dioctyl tin Acid esters, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, Bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc..(2) polyolefin catalyst for synthesizing：Such as Ziegler-Natta Catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, three It is fluorinated diethyl etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter ethyl chloride Change aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc..(3) CuAAC reactions by monovalence copper compound and Amine ligand shares concerted catalysis.Monovalence copper compound can be selected from Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc； Cu (I) complex compound is can be selected from, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；It can also be by simple substance Copper and cupric compound (such as CuSO4、Cu(OAc)2) in-situ preparation during the reaction；Wherein, the preferred CuBr of Cu (I) salt and Preferred CuBr (the PPh of CuI, Cu (I) complex compound3)3.Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yls) methyl] Amine (TBTA), three [(1- tertiary butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；Wherein, amine ligand preferred TBTA and TTTA.(4) thiol-ene catalytic reactions Agent：Photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyls phenylacetone, 2,2- dimethoxy -2- phenyl acetophenones etc.； Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl second Base amine etc..(5) catalysts between alkoxy borine and halogenated silanes：Suitable lewis acid catalyst, such as BCl3、 FeCl3、AlCl3、ZnCl2Deng.Catalyst amount used is not particularly limited, generally 0.01-2wt%.
Initiator in the auxiliary agent can cause monomer molecule to activate in polymerization process and generate free Base improves reaction rate, and reaction is promoted to carry out, and includes but are not limited to following any or appoints several initiators：Organic peroxy Compound, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, two hexamethylene of dicetyl peroxydicarbonate Bis- (4- tert-butylcyclohexyls) esters of ester, dicetyl peroxydicarbonate, tert butyl peroxy benzoate, tert-butyl hydroperoxide pivalic acid Ester, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, as azodiisobutyronitrile (AIBN), azo two are different Heptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred lauroyl peroxide of initiator, benzoyl peroxide Formyl, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1-1wt%.
Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, ensure that material can be smooth Ground carries out preparing processing and extends its service life, includes but are not limited to following any or appoints several antioxidant：Hindered phenol Class, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) butane, four [β-(3, 5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert butyl benzene Phenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization Isocyanates Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as the N, (β-naphthalene of N '-two Base) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thio-2 acid Dilauryl, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, three nonyl of phosphorous acid Phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Used Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent can prevent polymer samples from light aging occurs, extend its service life, It includes but are not limited to following any or appoints several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous Sour calcium；Ultra-violet absorber, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyls Base -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzotriazole, (the 2- hydroxyls of 2,4,6- tri- Base -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls；Pioneer's type is ultraviolet Light absorbers, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3,5- bis- tertiary fourths Base -4- benzylphosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer, such as the last of the ten Heavenly stems two Bis- (2,2,6,6- tetramethyl piperidines) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidines) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamates, N, N '-second, n-butyl dithiocarbamate nickel etc.；Wherein, Bis- (2,2,6,6- tetramethyl piperidines) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light stabilizer used is used Amount is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent enables to polymer samples during processing or use not due to heated Chemical change occurs, or delays these variations to achieve the purpose that prolong the service life comprising but it is not limited only to following A kind of or several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, stearic acid Lead, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate Mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；It is sub- Phosphoric acid ester, such as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphorous acid Ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Wherein, heat stabilizer is preferred Barium stearate, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not have It is particularly limited to, generally 0.1-0.5wt%.
Chain extender in the auxiliary agent can be such that strand expands with the reaction-ity group reaction on reactant molecule chain Exhibition, molecular weight increase comprising but be not limited only to following any or appoint several chain extenders：Polyalcohols chain extender, such as second two Alcohol, propylene glycol, diglycol, glycerine, trimethylolpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, to benzene Diphenol dihydroxyethyl ether (HQEE), resorcinol double hydroxyethyl ether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, Such as diaminotoluene, diamino dimethylbenzene, tetramethyl xylylen diamines, tetraethyl diphenyl methylene diamines, tetra isopropyl Hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminomethyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '- Diphenylmethanediamiand (MOCA), 3,5- dimethythiotoluene diamines (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1, 3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcamines chain extender, such as triethanolamine, triisopropanolamine, N, the bis- (2- of N '- Hydroxypropyl) aniline.Chain extender dosage used is not particularly limited, generally 1-20wt%.
Toughener in the auxiliary agent can reduce polymer samples brittleness, increase toughness, and it is strong to improve material carrying Degree comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-butadiene-styrene is copolymerized Resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylonitrile-butadiene-benzene second Alkene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-butadiene-benzene Ethylene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), benzene second Alkene-butadiene-styrene block copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS), Chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent can improve the interface characteristics of polymer samples and inorganic filler or reinforcing material Can, the viscosity of material melt is reduced in plastic processes, improves the dispersion degree of filler to improve processing performance, and then make system Product obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any or appoint several couplings Agent：Chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.；Wherein, The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
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%.
Lubricant in the auxiliary agent can improve the lubricity of polymer samples, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid, hydroxy stearic acid；Fat Esters of gallic acid, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type is such as hard Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamides；Fatty alcohol and polynary Alcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate, Zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used Agent dosage is not particularly limited, generally 0.5-1wt%.
Releasing agent in the auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean comprising but It is not limited only to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber etc.；Wherein, The preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5-2wt%.
Plasticizer in the auxiliary agent can increase the plasticity of polymer samples so that the hardness of polymer, mould Amount, softening temperature and brittle temperature decline, and elongation, flexibility and flexibility improve comprising but be not limited only to following any Kind appoints several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, phthalic acid two Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl Bis- (13) esters of ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthaldehyde Sour two (2- ethyls) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester, such as The own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy fat Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy soybean Oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate；Binary Alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat acid esters； Polyesters, as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester, phenyl alkylsulfonate, trimellitate, Citrate and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), two fourth of phthalic acid Ester (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5-20wt%.
Foaming agent in the auxiliary agent, can so that polymer samples foam pore-forming, to obtain light, heat-insulated, sound insulation, Flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Physical blowing agent, such as third Alkane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether, chlorine Methane, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, Ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-dinitroso is to benzene two Formamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, azo two are different Butyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide,-two sulphur of biphenyl -4,4 ' Acyl azide；Foamed promoter, as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, Lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, stearyl chloride, benzene diformazan Acyl chlorides, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, Thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, foaming agent is preferred Sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitros, N, N '- Dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used It is not particularly limited, generally 0.1-30wt%.
Dynamic regulation agent in the auxiliary agent can be promoted and adjust dynamic aggregation object dynamic, to be optimized Expected performance, be usually that free either free carboxyl group or can provide or receive electronics pair with free hydroxyl Compound includes but are not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc..Used Dynamic regulation agent dosage is not particularly limited, generally 0.1-10wt%.
The deleterious charge assembled in polymer samples can be guided or eliminated, makes it by the antistatic agent in the auxiliary agent Not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several antistatic agents：The moon from Subtype antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, to nonyl Diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, fatty amine Sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, dodecane Base trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second Inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, bis- polyoxyethylene of N- lauryls-N, N- Alkenyl-N- ethylphosphonic acids sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fat Sour ethylene oxide adduct, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride；It is high Molecule-type antistatic agent, such as the ethylene oxide propylene oxide addition product, polyene propionamide N- quaternary ammonium salts substituent, poly- 4- of ethylenediamine Vinyl -1- acetone yl pyridines phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, ten Eight alkyl dimethyl ethoxy quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).It is used Antistatic agent dosage be not particularly limited, generally 0.3-3wt%.
Emulsifier in the auxiliary agent can improve in the mixed with polymers liquid comprising auxiliary agent between various composition phases Surface tension is allowed to form uniform and stable dispersion or emulsion, is preferred for carrying out emulsion polymerization/crosslinking, packet It includes but is not limited only to following any or appoints several emulsifiers：Anionic, such as higher fatty acid salt, alkylsulfonate, alkyl Benzene sulfonate, Negel, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, Sulphation butyl ricinoleate salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, alkane Yl pyridines salt；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, such as poly alkyl alcohol Ethylene oxide ether, alkyl phenol polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, glycerin fatty Acid esters, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc.； Wherein, the preferred neopelex of emulsifier, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM).Emulsifier used is not particularly limited, generally 1-5wt%.
Dispersant in the auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into tiny particle And be suspended in liquid, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, while can also prevent particle Sedimentation and cohesion, form and stabilize suspension comprising but be not limited only to following any or appoint several dispersants：Anionic, Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as aliphatic alcohol polyethenoxy Ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Wherein, dispersant preferably 12 Sodium alkyl benzene sulfonate, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.Dispersant dosage used does not have It is particularly limited to, generally 0.3-0.8wt%.
Colorant in the auxiliary agent can make polymeric articles show required color, increase surface color and polish, It includes but are not limited to following any or appoints several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium Red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang The bright red R of red HF3C, the plastics and not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G、 Phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rose Rare essence, Oil Yellow etc.；Wherein, the selection of colorant need not be particularly limited to depending on color sample demand.Coloring used Agent dosage is not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent can make contaminated substance obtain the sparkling effect of similar fluorite, It includes but are not limited to following any or appoints several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline type, benzo Oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent CBS), bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene) Dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.
Delustering agent in the auxiliary agent when incident light being enabled to reach polymer surfaces, occurs diffusing reflection, generates low The matt and delustring appearance of gloss comprising but be not limited only to following any or appoint several delustering agents：Settle barium sulfate, dioxy SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred silica of delustering agent.Used disappears Photo etching dosage is not particularly limited, generally 2-5wt%.
Fire retardant in the auxiliary agent can increase the flame resistance of material comprising but be not limited only to following any Or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol Ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organohalogen compounds are such as high Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethanes, deca-BDE, penta decane of perchloro- ring；Inorganic combustion inhibitor, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as the anti-butylene of chlorendic anhydride, bis- (2,3- dibromopropyls) two Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.
Nucleating agent in the auxiliary agent can be accelerated crystalline rate, increase knot by the crystallization behavior of change polymer Brilliant density and promote fine grain size, reach and shorten material molding cycle, improves the product transparency, lustrous surface, tension The purpose of the physical mechanical properties such as intensity, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but be not limited only to Under it is any or appoint several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, silica, two Benzal D-sorbite and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, the preferred silica of nucleating agent, two benzals D-sorbite (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
Rheological agent in the auxiliary agent can ensure that polymer has good brushability and appropriate during film Coating thickness, the sedimentation of solid particle, can improve its redispersibility comprising but be not limited only to following when preventing storage A kind of or several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, lithium chloride, sulfuric acid Sodium, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, aluminium alkoxide, Titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanate derivates, acrylic acid Lotion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferred organobentonite of rheological agent, polyethylene wax, hydrophobic Modified alkaline swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, and one As be 0.1-1wt%.
Thickener in the auxiliary agent can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, from And meet various demands such as its stability and application performance during production, storage and use comprising but not It is only limitted to following any or appoints several thickeners：Lower-molecular substance, such as fatty acid salt, alkyldimethylamine oxide, aliphatic acid Single ethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut palm Sub- amido propyl betaine, titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, fine particle silica, colloid Aluminium, animal protein, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide Amine, polyvinyl pyrrolidone, polyethers etc.；Wherein, the preferred hydroxyl coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid are total Polymers.Thickener dosage used is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the auxiliary agent can ensure that the flat smooth of polymer coating film is uniform, improve film coated surface matter Amount improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Dimethyl silicone polymer, poly- methyl Phenyl siloxane, polyacrylate, organic siliconresin etc.；Wherein, the preferred dimethyl silicone polymer of levelling agent, polyacrylic acid Ester.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
In the preparation process of dynamic 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. the shrinking percentage of moulded products is reduced, Improve dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting the viscous of polymer Degree；3. meeting different performance requirement, polymer material impact strength and compressive strength, hardness, rigidity and modulus, raising are such as improved Wearability improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning light to stablize Property 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：It is inorganic non-metallic filler, metal packing, organic Filler.
The inorganic non-metallic filler includes but are not limited to following any or appoints several：Calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, carbon nanotube, molybdenum disulfide, slag, flue dust, wood powder and Shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, oil shale powder, expanded perlite Powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass microballoon, foam microspheres, glass powder, cement, glass Fiber, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, crystalline substance Palpus is equal.
The metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, gold etc. and its Powder, nano particle and the fiber of alloy.
The organic filler includes but are not limited to following any or appoints several：Fur, natural rubber, asbestos, worm Glue, chitin, chitosan, protein, raw lacquer, shell powder, silk, artificial silk, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, chitosan, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
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, Auxiliary agent, filler collectively constitute dynamic aggregation object compound system, but these add/be not necessarily all necessary using object.
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 at a suitable temperature in respective solvent or in common solvent.Hybrid reaction Suitable temperature is different because of raw material difference, and there is no particular limitation, is normally controlled in 0-200 DEG C, preferably 25-120 DEG C, more excellent Select 25-80 DEG C；Time difference due to raw material difference is mixed, there is no particular limitation, is normally controlled in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, at suitable temperature, usually 0-150 DEG C it Between, under preferably 25-80 DEG C of temperature condition, the time of specific length, preferably 0-48h are placed, polymer samples are obtained.This process In can select as needed retain solvent be made in the form of solution, emulsion, paste, glue etc. existing for polymer samples, or Person selects removing solvent that solid polymer sample existing for the forms such as membranaceous, blocky, foam-like is made.Dynamic is prepared in this approach When polymer, usually also needs to that initiator is optionally added in a solvent in a manner of polymerisation in solution to cause polymerization and obtain dynamic Polymer, or addition dispersant and oil-soluble initiator are configured to suspension in a manner of suspension polymerisation or slurry polymerization to draw Hair polymerization obtains dynamic aggregation object, or addition initiator and emulsifier are configured to emulsion in a manner of emulsion polymerization to cause Polymerization obtains dynamic aggregation object.Used polymerisation in solution, suspension polymerisation, slurry polymerization and emulsion polymerization method, be Those skilled in the art is known and widely used polymerization, can be adjusted according to actual conditions, here no longer in detail Thin expansion.
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.The suitable temperature of hybrid reaction is different because of raw material difference, and there is no particular limitation, is normally controlled in 0- 200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C；Time difference due to raw material difference is mixed, there is no particular limitation, It is normally controlled in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, be suitble to At a temperature of, usually between 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, place the time of specific length, preferably 0- 48h obtains polymer samples.When preparing dynamic aggregation object in this approach, usually also need to be optionally added into a small amount of initiator with The mode of melt polymerization or gas-phase polymerization obtains dynamic aggregation object to cause polymerization.Its used melt polymerization, gas-phase polymerization Method, be well known to those skilled in the art and widely used polymerization, can be adjusted according to actual conditions, Here it is no longer developed in details.
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, suitable extrusion temperature different, usually 0-280 DEG C, preferably 50-150 DEG C due to raw material difference.Reaction Product can directly be cut into suitable dimension after tape casting, or by obtained extrusion sample carry out it is broken after, using injection molding machine or Person's moulding press carries out sample preparation.Suitable injection temperature different, usually 0-280 DEG C, preferably 50-150 DEG C due to raw material difference, are fitted The injection pressure of conjunction different, preferably 60-150MPa due to raw material difference；Suitable molding temperature is different because of raw material difference, leads to It it is often 0-280 DEG C, preferably 25-150 DEG C, more preferable 25-80 DEG C, suitable clamp time is different because of raw material difference, usually 0.5-60min, preferably 1-10min, suitable molding pressure different, preferably 4-15MPa due to raw material difference.Batten can be set In suitable mold, at a suitable temperature, usually between 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, place special The time of measured length, preferably 0-48h obtain final polymer samples.
In the preparation process of dynamic aggregation object, the molar equivalent ratio of selected inorganic compounds of boron and silicon-containing compound It should be at range appropriate, carry out the molar equivalent ratio of other reactive groups of polymerized/cross-linked reaction, 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 Member 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.
By using dilatancy, dynamic possessed by dynamic aggregation object, making damping shock absorber can be applied to, used In the vibration isolation of various motor vehicles, mechanical equipment, bridge, building, it may also be used for prepare the speed lockup of road and bridge Device, for polymer material when vibrated, the big energy that can dissipate plays damping, can to effectively mitigate vibrations For making antidetonation shear plate or pulsating stress carrying tool；Also it can be applied to buffering package as energy-absorbing buffering material Material, athletic protective article, the police protective materials of surge guard product and army etc., to reduce article or human body outside Suffered vibrations and impact under force effect include the shock wave etc. of noise and explosion generation.Utilize inorganic boric acid estersil key Dynamic can also be used as shape-memory material, when the external force is removed, the shape that material generates in loading procedure Change can be restored；By dynamic reversibility possessed by dynamic aggregation object and rate of stressing dependence, it is quick to prepare stress The polymer material of sense type can be applied to prepare the magic toy and body-building material with stress/strain response, 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 be used for preparing and electronic component be bonded, is close The casting glue that envelope, embedding and coating are protected can be used for preparing the polymer with good plasticity and block glue, can design system The standby scratch resistant coatings for providing self-repair function are realized to extend the service life of coating to the long-acting anti-of basis material Corruption protection.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 as key can be sacrificed in use, a large amount of energy can be absorbed and assign polymer Material is with excellent toughness, it is hereby achieved that the polymer material that toughness is splendid, is widely used in military affairs, space flight, movement, energy The fields such as source, building.
Dynamic aggregation object material of the present invention is described further with reference to some specific implementation modes.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
By 1 molar equivalent trimethylborate and bis- (dimethyl hydroxyl silicon substrate) benzene of 10 molar equivalent 1,4- stirring state Lower that temperature is raised to 90 DEG C of progress after mixing, being added dropwise to a small amount of triethylamine, the reaction was continued, obtains compound 1a.
The dimethicone (average molecular weight is about 5000Da) of 15 molar equivalent both-end silicone hydroxyls sealing end, 6 moles are worked as Tetraethoxysilane, 2 molar equivalent compound 1a, dibutyl tin laurate (DBTDL is the 2% of raw material gross mass) is measured to fill Divide and be blended, cures 6 hours at room temperature, obtain a kind of dynamic aggregation containing common covalent cross-linking and inorganic boric acid estersil key Object.The 100 mass parts polymer and 5 mass parts graphenes are fully blended, resulting composition material, which removes, has good toughness And self-repairability, it may also be used for heat conduction, conduction, stress sensing etc..
Embodiment 2
The aqueous hydrochloric acid solution that pH is 2.5 is added in 1 molar equivalent trimethylethoxysilane, stirs at room temperature, waits hydrolyzing After completely, the boric acid of 10 molar equivalents is added, dehydrochlorination after the reaction was complete obtains compound 2a.By 2 molar equivalents (3- ammonia Base propyl) dimethylethoxysilane be added pH be 2.5 aqueous hydrochloric acid solution, stir at room temperature, after hydrolysis completely after, be added 1 Molar equivalent compound 2a, dehydrochlorination after the reaction was complete, obtains compound 2b.
Weigh the polyethylene glycol (average molecular weight is about 500Da) and 4 molar equivalents of 5 molar equivalent both ends carboxy blockings Compound 2b, with 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline (EEDQ) be used as condensing agent, be obtained by the reaction containing whether there is or not The line style dynamic covalent polymer of machine boric acid estersil key.
The dynamic covalent polymer that 100 mass parts contain inorganic boric acid estersil key is swollen in into the crosslinking containing 20 mass parts It spends in the solvent of the dimethyl silicone polymer more than gel point, removes solvent after being fully blended, obtain a kind of dynamic of the present invention Polymer.The dynamic aggregation object has sensitive dilatancy, can be used for preparing speed lockup's device of road and bridge, can also be by it Lotion is made to be applied on textile, is fabricated to shock resistance energy-absorbing protective articles.
Embodiment 3
By boric acid and acrylic dimethylchlorosilane according to molar ratio 1:3 mixing, using triethylamine as catalyst, at 80 DEG C 12 hours obtained ends of reaction carry the boric acid estersil compound 3a of double bond.Using chloroplatinic acid as catalyst, a certain amount of methyl is contained Hydrogen silicone oil (average molecular weight is about 1500Da) and compound 3a react 3 hours in cyclohexanone at 90 DEG C, control silicon hydrogen with The molar ratio of compound 3a is about 3:1, it obtains with the inorganic crosslinked polysiloxanes of boric acid estersil key.
The hydroxy-end capped dimethyl-silicon of the trifluoro propyl silicone oil and 50 mass parts both ends that take 100 mass parts both ends hydroxy-end capped The mixture of oil is blended, and polymerize obtained from being crushed with the crosslinked polysiloxanes of inorganic boric acid estersil key obtained by 50 mass parts Composition granule, it is evenly dispersed wherein, add 5 mass parts DBTDL and a certain amount of methyltrimethoxysilane, and keep in raw material The molar ratio of silicone hydroxyl and methoxy silicon substrate is 1:1, reaction solidification 12 hours, obtains a kind of dynamic aggregation of the present invention at room temperature Object.The product has excellent toughness, can be used for manufacturing a kind of scratch resistant coatings of selfreparing or the group for electronic product The casting glue of the sealing waterproof of part.
Embodiment 4
Using allyl alcohol as initiator, stannous octoate is catalyst, and it is alkenyl one to cause 6-caprolactone ring-opening polymerisation to obtain one end End is hydroxy-end capped polycaprolactone, then itself and acroleic acid esterification are obtained the polycaprolactone that both ends are alkenyl sealing end.By gained Both ends be alkenyl sealing end polycaprolactone and γ-mercaptopropyl trimethoxysilane using AIBN as initiator, triethylamine is to urge Silane-modified polycaprolactone 4a is obtained by the reaction in agent.
By above-mentioned silane-modified polycaprolactone and trimethylborate according to the molar ratio 1 of Si-OR groups and B-OR groups: 1 mixing, is calculated as 100 mass parts, is added that 10 parts by mass of cellulose are nanocrystalline, swell in the degrees of cross linking of 30 mass parts gel point with On poly- methyl trifluoro propyl siloxanes.Mixture is warming up to 80 DEG C after mixing, a small amount of deionized water is added, is stirring Polymerisation is carried out under state, obtains a kind of dynamic aggregation object of the present invention.
The product can be used for requirement damping, impact resistance, field that is warping strength and requiring sufficient intensity, as auto parts, Retractility telephone cord, hydraulic hose, driving belt, rotational forming tire, gear, flexible joint, noise reduction gear, elevator are slided Road, the corrosion-proof wear-resistant material in chemical industry equipment pipeline valve, antidetonation shear plate, pulsating stress carrying tool etc..
Embodiment 5
Using methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and n-butyl acrylate as monomer, the molar ratio of the two is controlled It is 1:15, the copolymer of methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and n-butyl acrylate is made by free radical polymerization (molecular weight is about 4000Da).
By above-mentioned copolymer and trimethylborate according to the molar ratio 1 of Si-OR groups and B-OR groups:1 mixing, is calculated as 100 mass parts swell in polychlorostyrene phenyl methyl siloxane of the 20 mass parts degrees of cross linking more than gel point, are warming up to 80 DEG C of mixing After uniformly, a small amount of deionized water is added, is reacted under stirring, obtains a kind of dynamic aggregation object of the present invention.By 100 Aftershaping is blended with 5 mass parts carbon nanotubes in mass parts resulting polymers, obtains corresponding product, can be used for stress induction.
Embodiment 6
With 1 molar equivalent 4,4'- azos bis- (4- cyano amylalcohols) are that initiator draws using 4- amylene-1-ols as chain-transferring agent 4 molar equivalent methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and the copolymerization of 60 molar equivalent n-butyl acrylates are sent out, obtain two The polyacrylate of terminal hydroxy group sealing end.
By the hydroxy-end capped poly- methyl in the hydroxy-end capped acrylate in the both ends obtained by 6 molar equivalents, 7 molar equivalent both ends Phenyl siloxane (average molecular weight is about 2000Da), 10 molar equivalent toluene di-isocyanate(TDI)s (TDI), 2 molar equivalent triphens Methane triisocyanate reacts under the catalysis of dibutyl tin laurate (DBTDL), obtains containing trimethoxy silicon substrate side group Common covalent cross-linking polymer.
By the polymer of above-mentioned gained and trimethylborate according to the molar ratio 1 of Si-OR groups and B-OR groups:1 mixing, It is warming up to 80 DEG C after mixing, a small amount of deionized water is added, condensation reaction is carried out under stirring, the present invention is prepared A kind of dynamic aggregation object.Resulting polymers have splendid toughness, and can be used for manufacturing has self-repair function anti-tear Adhesive blocks glue.
Embodiment 7
By styrene, styrene ethyl trimethoxy silane and according to molar ratio 10:1 is mixed, with two isobutyl of azo Nitrile (AIBN) is initiator, and the linear polystyrene containing siloxanes side group is made using by free-radical polymerized.
It weighs a certain amount of above-mentioned polystyrene containing siloxanes side group and trimethylborate is dissolved in toluene, keep Si-OR The molar ratio of group and B-OR groups is 2:1, it is heated to 60 DEG C and is dissolved and then be added catalyst DBTDL by stirring, Mixed liquor is placed in suitable mold drying 24 hours in 80 DEG C of vacuum drying ovens, a kind of dynamic for finally obtaining the present invention is poly- Close object.
Resulting polymers are packed into mold, are placed in autoclave, supersaturated carbon dioxide is passed through.Pressurized, heated is extremely Decompression makes its expanded foamed molding after 160 DEG C, 12 minutes, and corresponding foamed product is obtained after demoulding.The polymer has certain Intensity, toughness, can be used for manufacture packaging material, heat preserving and insulating material, insulating materials, sound insulation and noise reduction material, dalle Deng.
Embodiment 8
It is amino-terminated polyisobutene (average molecular weight is about 1500Da) and 2 molar equivalents by 1 molar equivalent both ends Isophorone diisocyanate is reacted in dichloromethane, adds 2 molar equivalent 3- aminopropyl diformazans after complete reaction Base methoxy silane obtains the polyisobutene that both ends are blocked with dimethyl methyl oxosilane after the reaction was complete.By single-ended to be amino-terminated Polyisobutene (average molecular weight is about 1500Da) and equimolar equivalent isophorone diisocyanate it is anti-in dichloromethane It answers, adds equimolar equivalent 3- dimethyl methoxy silanes after completely, obtained after the reaction was complete single-ended with diformazan The polyisobutene of base methoxy silane sealing end.Polyisobutene that both ends obtained by 1 molar equivalent are blocked with dimethyl methyl oxosilane, 2 Molar equivalent is single-ended to be fully blended with the polyisobutene and 1 molar equivalent boric acid of dimethyl methyl oxosilane sealing end, is obtained by the reaction and is contained There is the branched dynamic aggregation object of inorganic boric acid estersil key.
By dynamic aggregation object, 100 mass parts Polymethyl methacrylates and a certain amount of both ends obtained by 100 mass parts (average molecular weight is about 1500Da to the polyisobutene of sulfydryl sealing end, and it is 1 to keep sulfydryl and polysiloxanes medium vinyl molar ratio: 1) it is fully blended with 0.01 mass parts benzil dimethyl ketal (BDK).It reacts under the irradiation of ultraviolet lamp, obtains the present invention's A kind of dynamic aggregation object.Large deformation can occur under smaller pressure or tensile force effect for the dynamic aggregation object, but quickly draw But it can show high resiliency when stretching or beating, it can be as toy and body-building material with magic stressed effect.
Embodiment 9
3 molar equivalent methyclyloxypropyl dimethylchlorosilanes and 1 molar equivalent boric acid are dissolved in tetrahydrofuran, are dripped Enter a small amount of water and acetic acid, reacted at 50 DEG C, obtains trifunctional acrylic ester monomer 9a.By trifunctional acrylic ester monomer The carry out emulsion copolymerization of 9a and butyl acrylate, it is 1 to keep the molar ratio of two monomers:10, it obtains being based on butyl polyacrylate Dynamic crosslinking polymer beads.
By the hydroxy-end capped dimethicone in 1 molar equivalent both ends (average molecular weight is about 1000Da) and 2 molar equivalents Methacrylic acid reacts under the catalysis of DCC and DMAP, obtains macromolecules cross-linking agent.Weigh 10 molar equivalent methyl acrylates with 1 molar equivalent macromolecules cross-linking agent, gross mass are calculated as 100 mass parts, the dynamic with the butyl polyacrylate obtained by 20 mass parts Cross-linked polymer particle and the photoinitiator b DK of 0.5 mass parts are fully blended, and pour into the glass board mould for accompanying silica gel pad In, ultraviolet radioactive 4 hours in UV crosslinking instrument are placed on, a kind of dynamic aggregation Tetramune of the present invention is obtained.It is prepared by the polymer At film, show more excellent comprehensive performance, certain tensile strength and good tear resistance, and can carry out compared with The stretching of big degree.Such dynamic aggregation object can be applied to prepare function film, or can be as the pad pasting of automobile and furniture It uses, also can be used as stretch wrappers and used.
Embodiment 10
By the line style polyvinyl acetate of a certain amount of partial hydrolysis, (average molecular weight is about 2000Da, and degree of hydrolysis is about 5%) and dimethyldimethoxysil,ne carries out alkoxy exchange reaction under the catalysis of sodium ethoxide, holding hydroxyl and methoxyl group Molar ratio is 1:1, obtain the common covalent cross-linking polymer based on polyvinyl acetate.
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 Stirring is dissolved, and a small amount of water is added, and the reaction was continued 4 hours, obtains a kind of trivinyl compound containing boric acid estersil key 10a.By 1 molar equivalent 10a, 10 molar equivalents 1,2- dithioglycols and 0.1 molar equivalent photochemical catalyst BDK are blended, ultraviolet It is fully reacted under the irradiation of light, converts the alkenyl of compound end to sulfydryl, obtain compound 10b.
The polyethylene glycol (average molecular weight is about 2000Da) that 3 molar equivalent both ends are blocked with alkenyl and 2 molar equivalents Compound 10b is blended, and is calculated as 100 mass parts and 0.1 molar equivalent photochemical catalyst BDK is swollen in jointly obtained by 100 mass parts Common covalent cross-linking polymer based on polyvinyl acetate, fully reacts under the irradiation of ultraviolet light, obtains the one of the present invention Kind dynamic aggregation object.Resulting polymers are swollen in into deionized water, obtain corresponding dynamic aggregation object hydrogel.The dynamic aggregation The excellent self-repairability that object hydrogel has can be used as the buffering package with self-repair function.
Embodiment 11
By the methyl phenyl silicone oil (average molecular weight is about 3000Da) of 95 mass parts both-end silicone hydroxyls sealing end, 5 mass parts Containing hydrogen silicone oil, 0.5 mass parts quaternary amine alkali, 8 mass parts nano-calcium carbonates and 20 mass parts polyvinylpyrrolidone particles are fully total It is mixed, it swells in 40 mass parts embodiments 1 in the obtained dynamic aggregation object containing common covalent cross-linking and boric acid estersil key. Gained mixture is placed in mold, is reacted in 190 DEG C, a kind of dynamic aggregation Tetramune of the present invention is obtained.Gained is poly- Composition powder also has certain hygroscopicity, can be used as protecting against shock protection materials in addition to good intensity, toughness, wearability It uses.
Embodiment 12
The limonene oxide extracted from orange peel is issued with 100psi carbon dioxide in the catalytic action of beta-diimine zinc Raw polymerisation, obtains makrolon PLimC.By above-mentioned makrolon PLimC and γ-mercapto hydroxypropyl methyl dimethoxysilane, Two (2- mercaptoethyls) adipate esters are 5 according to double bond group and sulfydryl ratio:4:1 mixing, is added the AIBN of 0.5wt%, instead The makrolon containing common covalent cross-linking and silicone hydroxyl presoma should be made.
Weigh three (the 2- methoxyl groups of makrolon and 20 mass parts that the above-mentioned side group of 100 mass parts contains silicone hydroxyl presoma Ethyl) borate, it is thoroughly mixed uniformly, after being warming up to 80 DEG C, a small amount of deionized water is added, is carried out under stirring A kind of dynamic aggregation object of the present invention is prepared in polymerisation.100 mass parts of gained dynamic aggregation object are swollen in into Silicon Containing Hydrogen Oil and 150 mass parts of hydroxy silicon oil carry out cross-linking reaction under the catalysis of quaternary amine alkali in 190 DEG C, and the one kind for obtaining the present invention is dynamic State polymer.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 13
By boric acid and acrylic dimethylchlorosilane according to molar ratio 1:3 mixing, using triethylamine as catalyst, at 80 DEG C 12 hours obtained ends of reaction carry the boric acid estersil compound 13a of double bond.By 1 molar equivalent compound 13a and 3 molar equivalents 3- mercaptopropyltriethoxysilanes and 0.1 molar equivalent photochemical catalyst BDK react under the irradiation of ultraviolet light, obtain compound 13b.Hydroxyl-terminated injecting two methyl siloxane, containing hydrogen silicone oil, dimethyl diethoxysilane are fully blended, are catalysis with DBTDL Agent, vacuum defoamation cure 3 hours at room temperature after 3 minutes, obtain a kind of containing common covalent cross-linking and inorganic boric acid estersil key Dynamic aggregation object.It weighs the hydroxy-end capped dimethyl silicone polymer (average molecular weight 1000Da) in 20 molar equivalent both ends, 15 rub The hydroxy-end capped polybutyl methacrylate (average molecular weight 3000Da) in your equivalent both ends, 6 molar equivalent glycerine, 44 moles work as TDI is measured, each component gross mass is calculated as 100 mass parts, the dynamic aggregation object of the above-mentioned gained of 100 mass parts is swollen in, in DBTDL Catalysis under, be obtained by the reaction in 80 DEG C the present invention a kind of dynamic aggregation object.Gained dynamic aggregation object has good shock resistance Barrier propterty can be used for preparing bulletproof glass squeegee or other surge guard products.
Embodiment 14
Polynorbornene (molecular weight about 20000Da) and thiopurine methyltransferase methyldiethoxysilane, 1,4- succinimide mercaptans are pressed It is 100 according to double bond and sulfydryl ratio:25:5 mixing, using benzoin dimethylether as photoinitiator, ultraviolet light is light source, is passed through a little It hits reaction and the polynorbornene for containing ethyoxyl siloxane group containing common covalent cross-linking and side group is made.
The polynorbornene obtained by 100 mass parts and a certain amount of three methyl borate are weighed, Si-OR groups and B-OR are kept The molar ratio of group is 1:1, it heats the mixture to 60 DEG C and is dissolved by stirring, add a small amount of 20% acetic acid aqueous solution The reaction was continued 4 hours, obtains a kind of dynamic aggregation object containing common covalent cross-linking and inorganic boric acid estersil key simultaneously.
Weigh the amino-terminated polyphenyl methyl siloxane (average molecular weight 1500Da) in 10 molar equivalent both ends, 20 moles The amino-terminated polyisobutene (average molecular weight 2000Da) in equivalent both ends, 10 molar equivalent melamines, 45 molar equivalents six Each component gross mass is calculated as 100 mass parts, 15 mass parts montmorillonites is added, swell in 200 mass by methylene diisocyanate The dynamic aggregation object of the above-mentioned gained of part, is obtained by the reaction a kind of dynamic aggregation object of the present invention.Gained dynamic aggregation object has fine Defense of resistance to impact performance and anti-flammability, can be used for preparing army and police's protective article with the functions such as burn-proof and explosion prevention.
Embodiment 15
The TDI of 3- dimethyls methoxy silane and equimolar equivalent is reacted in anhydrous methylene chloride, is obtained One end is the compound of isocyanate group.By compound obtained by 2 molar equivalents and the hydroxy-end capped poly- β-hydroxyl in 1 molar equivalent both ends Base butyrate (PHB) reacts under the catalysis of DBTDL, obtains the PHB that both ends are methoxy silicon substrate.It weighs obtained by 2 molar equivalents PHB, 5 molar equivalent tert-butyl chloro-silicanes and 3 molar equivalent boric acid are heated to 60 DEG C and are stirred to react 8 hours, obtain Non-crosslinked dynamic aggregation object containing inorganic boric acid estersil key.
PHB, benzene dimethylene diisocyanate and the glycerine for taking a certain amount of both ends hydroxy-end capped keep PHB, two isocyanides The molar ratio of acid esters and glycerine is about 10:13:2.01, gross mass is calculated as 100 mass parts, and the DBTDL of 0.1 mass parts is added, in 80 DEG C of reactions, obtain the cross-linked type polyurethane based on polyester.
Dimethicone, benzene dimethylene diisocyanate and the glycerine for taking a certain amount of both ends hydroxy-end capped keep poly- The molar ratio of ethylene glycol, diisocyanate and glycerine is about 10:13:2.01, gross mass is calculated as 100 mass parts, and 0.1 mass is added Part DBTDL, non-crosslinked dynamic aggregation object and 50 mass parts biodegradable polyesters tiny balloons obtained by 100 mass parts, altogether With the cross-linked type polyurethane based on polyester swollen in obtained by 50 mass parts a kind of dynamic of the present invention is obtained in 80 DEG C of reactions Foam of polymers.
The dynamic aggregation object foam can be used as the amortizing packaging material of breakables, can heat-insulating and shock-absorbing, while having good Biodegradability.
Embodiment 16
The polypropylene (average molecular weight is about 3000Da) and and carboxylic of both ends carboxy blocking and single-ended carboxy blocking are taken respectively Base equimolar equivalent 3- dimethyl methoxy silanes, using EEDQ as condensing agent, at room temperature in dark, in dichloromethane Alkane/methanol volume ratio is 2:1 in the mixed solvent is reacted 16 hours, respectively obtains both ends and single-ended with dimethyl methyl oxosilane base The polypropylene of group's sealing end.The polypropylene of 3 molar equivalent two ends sealeds, the polypropylene of the single-ended sealing end of 6 molar equivalents and 4 moles are worked as Trimethylborate mixing is measured, after being warming up to 80 DEG C, the deionized water of quality 2% is added, condensation reaction is carried out under stirring, A kind of branching type dynamic aggregation object containing inorganic boric acid estersil key is prepared.
By hydroxy-end capped 100 mass parts of Methyl Octyl silicone oil in 100 mass parts of gained branching type dynamic aggregation object, both ends and 10 mass parts of hydroxy silicon oil, 40 mass parts of dimethyldimethoxysil,ne, 20 mass parts of silester are blended, and swell in 200 matter Polypropylene of part degree of cross linking more than gel point is measured, at room temperature, a kind of solidification crosslinking 8 hours, the dynamic for obtaining the present invention is gathered Close object.The dynamic aggregation object can be used as shape-memory material use.
Embodiment 17
By 3- dimethyls methoxy silane and Adipoyl Chloride according to molar ratio 2:1 mixing, using triethylamine as urging Agent is reacted in anhydrous methylene chloride, obtains compound 17a.Weigh 12 molar equivalent compound 17a, the tertiary fourth of 6 molar equivalents Base dimethylchlorosilane and 10 molar equivalent boric acid are heated to 60 DEG C and are stirred to react 8 hours, obtained containing Inorganic Boron after crushing The crosslinking dynamic covalent polymer particle of sour estersil key.
Dimethicone (average molecular weight is about 2000Da), 1 molar equivalent for taking 20 molar equivalent both ends amino-terminated The amino methyl silicone oil (average molecular weight is about 1500Da) and a certain amount of cyclohexanedimethyleterephthalate two that side group contains amino are different Cyanate, it is 1 to keep the molar ratio of amino and isocyanate group:1, above-mentioned each component is amounted into 100 mass parts.100 are taken again Polymer beads and the 50 mass parts degrees of cross linking containing inorganic boric acid estersil key obtained by mass parts more than gel point poly- two Above-mentioned each component and 50 parts by mass Methylene chloride and 30 mass parts water are quickly uniformly mixed and are placed in mold by methylsiloxane In in free foaming, obtain a kind of dynamic aggregation object foamed product of the present invention.The foamed product has good flexibility, can Large range of stretching is carried out, shock resistance is excellent, can be used as athletic protective article.
Embodiment 18
Using benzoyl peroxide amine as initiator, using acrylonitrile and compound 9a as monomer, acrylonitrile and compound are kept The molar ratio of 9a is about 10:1, the crosslinking dynamic covalent polymer particle based on polyacrylonitrile is made using suspension polymerization.
By the hydroxy-end capped phenyl methyl silicone oil in the hydroxy-end capped polystyrene in both ends, both ends, DBTDL, diisocyanate With polypropylene of the crosslinking dynamic covalent polymer granules swell in the degree of cross linking more than gel point based on polyacrylonitrile of gained It in nitrile, is fully reacted at 80 DEG C, obtains a kind of dynamic aggregation object of the present invention.By the dynamic aggregation object of gained and etc. quality 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquids are fully blended together, obtain corresponding dynamic aggregation object ionic gel. This ionic liquid gel stability is good, mechanical property is strong, excellent shock resistance, can be used as defense of resistance to impact pad or damping subtracts Rheopexy glue uses.
Embodiment 19
By trimethylborate and dimethyl methyl oxygroup -3- butine silane according to molar ratio 1:3 mixing, are heated to 60oC and pass through After stirring is dissolved, a small amount of water is added, and the reaction was continued 4 hours, obtains a kind of alkynyl chemical combination containing inorganic boric acid estersil key Object 19a.
By branching type polyvinyl chloride and reaction of sodium azide, chlorine atom and the molar ratio of sodium azide in side group is kept to be about 15:1, obtain the modified polyvinyl chloride that part side group is azido.Gained modified polyvinyl chloride and compound 19a are dissolved in tetrahydrochysene Furans, it is 1 to keep the molar ratio of azido and alkynyl:1, under the catalysis of cuprous iodide and pyridine, reacted at 35 DEG C.It waits for anti- Should completely after, the modified polyvinyl chloride containing nitrine side group of quality and a certain amount of two silicon of diacetylene tetramethyl such as add Oxygen alkane, it is 1 to keep the molar ratio of azido and alkynyl:1, the reaction was continued, obtains the dynamic polychlorostyrene with the 8th kind of network structure Ethylene.The modified polyvinyl chloride containing nitrine side group of quality and a certain amount of two silica of diacetylene tetramethyl such as add Alkane, it is 1 to keep the molar ratio of azido and alkynyl:1, the reaction was continued, obtains a kind of dynamic polyvinyl chloride of the present invention.
By 100 mass parts of dynamic polyvinyl chloride of gained, 70 mass parts of epoxidized soybean oil, 50 mass parts of tricresyl phosphate It is uniformly mixed, compression molding obtains corresponding dynamic aggregation object plasticizer gel product.The product is anti-with good shock resistance Performance is protected, damper, padded coaming, toughness material are can be used for.
Embodiment 20
By the crosslinking agent 2- methyl -2- acrylic acid -1,2- second two of the butyl methacrylate of 100 mass parts and 5 mass parts Alcohol ester is swollen in crosslinked polydimethyl siloxanes of the degree of cross linking more than gel point, under the initiation of photoinitiator and ultraviolet light Polymerization, obtains polybutyl methacrylate-polydimethylsiloxanepolymer polymer alloy.
Both ends are subjected to hydrogenation reaction with the polycyclic octene of carboxy blocking, obtain the polyethylene that both ends are carboxyl.Take 1 mole Polyethylene obtained by equivalent and 2 molar equivalent 3-aminopropyltriethoxysilane, it is dark at room temperature using EEDQ as condensing agent In methylene chloride/methanol volume ratio be 2:1 in the mixed solvent is reacted to obtain gathering with what triethoxysilane blocked for 16 hours Ethylene.
By the polyethylene of above-mentioned gained and triethyl borate according to the molar ratio 1 of Si-OR groups and B-OR groups:1 mixing, 100 mass parts are calculated as, the polymer alloy of gained is swollen in, is warming up to 80 DEG C after mixing, a small amount of deionized water is added, Condensation reaction is carried out under stirring, and a kind of dynamic crosslinking polymer is prepared.
By etc. quality above-mentioned polymer alloy and dynamic crosslinking polymer be blended and compression molding, obtain corresponding dynamic Polymer product.The product has excellent toughness, can be used for manufacturing a kind of selfreparing elastomer.
Embodiment 21
By 1 molar equivalent compound tetramethyl divinyl disiloxane, 2 molar equivalent 1- thioglycerols and 0.1 mole Equivalent BDK reacts under the irradiation of ultraviolet light, obtains compound 21a.Take 1 molar equivalent 21a, 2 molar equivalent glycerine, 30 moles The hydroxy-end capped polycaprolactone in equivalent both ends (average molecular weight is about 2000Da) and 35 molar equivalent diphenyl methane, two isocyanide The gross mass of the above component is calculated as 100 mass parts by acid esters, and swells in poly- second of the 50 mass parts degrees of cross linking more than gel point It in alkene, is reacted 3 hours in 80 DEG C under the catalysis of TDBDL, then is warming up to 120 DEG C and reacts 1 hour, obtained simultaneously containing there are two general The polymer alloy of valence cross-linked network in all.
(average molecular weight is about the polycaprolactone for taking 3 molar equivalent 17b, 20 molar equivalent both ends hydroxy-end capped 2000Da), the 8 molar equivalent tert-butyl alcohols and 30 molar equivalent methyl diphenylene diisocyanates, by the gross mass meter of the above component For 100 mass parts, the polymer of the above-mentioned gained of 50 mass parts is swollen in jointly with 50 parts by mass Methylene chloride and 30 mass parts water Alloy, quickly mixing is placed in mold in 80 DEG C of free foamings 3 hours under the catalysis of DBTDL, then is warming up to 120 DEG C of solidifications 1 hour, obtain a kind of dynamic aggregation object foamed product of the present invention.
Resulting polymers product shock resistance is excellent, can be used as impact-resistant bumper.
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 (15)

1. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that described is dynamic with hybrid cross-linked structure Include a common covalent cross-linking network in state polymer, the common covalent cross-linking network skeleton is polysiloxanes chain structure； Wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein covalent any one B in inorganic boric acid estersil key of the dynamic Atom is connect with three-O-, and at least partly former from the different Si in at least two different B-O-Si keys based on different B atoms The linker of son connection is former containing the carbon on dynamic covalent polymer main chain backbone in linker L, the linker L Son.
2. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the tool There is the dynamic aggregation object of hybrid cross-linked structure that there is one kind in four kinds of network structures as described below：
In one such network structure, the described dynamic aggregation object with hybrid cross-linked structure only there are one cross-linked network, Contain the covalently inorganic boric acid estersil key crosslinking of common covalent cross-linking and dynamic in the network simultaneously, it is solidifying that common covalent cross-linking reaches it It is more than glue point；Wherein, the common covalent cross-linking network skeleton is polysiloxanes chain structure；The covalent inorganic boric acid silicon of the dynamic Any one B atom connect to form three B-O-Si keys with three-O- in ester bond, and at least partly from least two based on different The linker of different Si atoms connection in the different B-O-Si keys of B atoms is to contain to be in linker L, the linker L Carbon atom on dynamic covalent polymer main chain backbone；
In another kind network structure therein, only there are one networks for the dynamic aggregation object with hybrid cross-linked structure, should Network only has common covalent cross-linking, and common covalent cross-linking therein reaches gel point or more, and is wherein dispersed with noncrosslinking Dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, the common covalent cross-linking network skeleton is poly- silicon Oxygen alkane chain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly Linker from the different Si atoms connection in at least two different B-O-Si keys based on different B atoms is linker L, described Contain the carbon atom on dynamic covalent polymer main chain backbone in linker L；
In another kind network structure therein, only there are one networks for the dynamic aggregation object with hybrid cross-linked structure, should Network only has common covalent cross-linking, and common covalent cross-linking therein reaches gel point or more, and is wherein dispersed with dynamically total The crosslinked dynamic covalent polymer particle of the inorganic borate key of valence；Wherein, the common covalent cross-linking network skeleton is poly- silica Alkane chain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly with The linker of different Si atoms connection in at least two different B-O-Si keys based on different B atoms is linker L, the company It connects in base L containing the carbon atom on dynamic covalent polymer main chain backbone；
In another kind network structure therein, the dynamic aggregation object with hybrid cross-linked structure is containing there are two networks；1st Common covalent cross-linking is contained only in network；Its gel is reached with the dynamic crosslinking that covalently inorganic boric acid estersil key is formed in 2nd network Or more, and without common covalent cross-linking more than gel point；Wherein, the common covalent cross-linking network skeleton is polysiloxanes Chain structure；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly with extremely The linker of different Si atoms connection in few two different B-O-Si keys based on different B atoms is linker L, the connection Contain the carbon atom on dynamic covalent polymer main chain backbone in base L.
3. the dynamic aggregation object according to claim 1 with hybrid cross-linked structure, which is characterized in that described having is miscellaneous The dynamic aggregation object for changing cross-linked structure contains one or more kinds of hydrogen bond groups, and it is poly- that the hydrogen bond group is present in crosslinking It closes in object cross-linked network chain backbone or in non-cross-linked polymer main chain backbone, or exists simultaneously in cross-linked polymer cross-linked network chain In skeleton and non-cross-linked polymer main chain backbone.
4. the dynamic aggregation object according to claim 3 with hybrid cross-linked structure, which is characterized in that described having is miscellaneous The hydrogen bond group that the dynamic aggregation object of change cross-linked structure contains contains at least one of following constituent：
5. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that described is dynamic with hybrid cross-linked structure Include a common covalent cross-linking network in state polymer, the common covalent cross-linking network skeleton is siliceous heterochain structure, and When in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20；While its In include the covalent inorganic boric acid estersil key of dynamic, wherein the dynamic covalently in inorganic boric acid estersil key any one B atom with Three-O- connections, and at least partly connect from least two with the different Si atoms of the different B-O-Si keys based on different B atoms Linker be in linker L, the linker L containing the carbon atom on the dynamic covalent polymer main chain backbone.
6. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 5, which is characterized in that the tool There is the dynamic aggregation object of hybrid cross-linked structure that there is one kind in four kinds of network structures as described below：
In one such network structure, the described dynamic aggregation object with hybrid cross-linked structure only there are one cross-linked network, Contain the covalently inorganic boric acid estersil key crosslinking of common covalent cross-linking and dynamic in the network simultaneously, it is solidifying that common covalent cross-linking reaches it It is more than glue point；Wherein, the common covalent cross-linking network skeleton is siliceous heterochain structure, and is located when containing in the siliceous heterochain When the carbochain section of cross-linked network skeleton, carbon atom therein is no less than 20；The dynamic is covalently in inorganic boric acid estersil key Any one B atom connect to form three B-O-Si keys with three-O-, and is at least partly based on different B atoms from least two Different B-O-Si keys in different Si atoms connection linker be linker L, the linker L in containing in dynamic altogether Carbon atom on valence main polymer chain skeleton；
In another kind network structure therein, only there are one networks for the dynamic aggregation object with hybrid cross-linked structure, should Network only has common covalent cross-linking, and common covalent cross-linking therein reaches gel point or more, and is wherein dispersed with noncrosslinking Dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, the common covalent cross-linking network skeleton is siliceous Heterochain structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly at least The linker of different Si atoms connection in two different B-O-Si keys based on different B atoms is linker L, the linker Contain the carbon atom on dynamic covalent polymer main chain backbone in L；
In another kind network structure therein, only there are one networks for the dynamic aggregation object with hybrid cross-linked structure, should Network only has common covalent cross-linking, and common covalent cross-linking therein reaches gel point or more, and is wherein dispersed with dynamically total The crosslinked dynamic covalent polymer particle of the inorganic borate key of valence；Wherein, the common covalent cross-linking network skeleton is containing sila Chain structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20 It is a；Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly at least two The linker of different Si atoms connection in a different B-O-Si keys based on different B atoms is linker L, the linker L In contain the carbon atom on the dynamic covalent polymer main chain backbone；
In another kind network structure therein, the dynamic aggregation object with hybrid cross-linked structure is containing there are two networks；1st Common covalent cross-linking is contained only in network；Its gel is reached with the dynamic crosslinking that covalently inorganic boric acid estersil key is formed in 2nd network Or more, and without common covalent cross-linking more than gel point；Wherein, the common covalent cross-linking network skeleton is siliceous heterochain Structure, and when in the siliceous heterochain containing the carbochain section in cross-linked network skeleton, carbon atom therein is no less than 20； Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and at least partly at least two bases The linker of different Si atoms connection in the different B-O-Si keys of different B atoms is to contain in linker L, the linker L There is the carbon atom on dynamic covalent polymer main chain backbone.
7. the dynamic aggregation object according to claim 5 with hybrid cross-linked structure, which is characterized in that described having is miscellaneous The dynamic aggregation object for changing cross-linked structure contains one or more kinds of hydrogen bond groups, is present in cross-linked polymer cross-linked network In chain backbone or in non-cross-linked polymer main chain backbone, or exist simultaneously in cross-linked polymer cross-linked network chain backbone and non-crosslinked In main polymer chain skeleton.
8. the dynamic aggregation object according to claim 7 with hybrid cross-linked structure, which is characterized in that described having is miscellaneous The hydrogen bond group that the dynamic aggregation object of change cross-linked structure contains contains at least one of following constituent：
9. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that described is dynamic with hybrid cross-linked structure State polymer includes at least two common covalent cross-linking networks, and at least one common covalent cross-linking network skeleton is poly- silica Alkane chain or siliceous heterochain structure；It wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein the covalent Inorganic Boron of dynamic Any one B atom is connect with three-O- in sour estersil key, and at least partly from least two differences based on different B atoms The linker of different Si atoms connection in B-O-Si keys is in linker L, the linker L containing in dynamic covalently polymerization Carbon atom on owner's chain backbone.
10. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 9, which is characterized in that described Dynamic aggregation object with hybrid cross-linked structure is with one kind in four kinds of network structures as described below：
In one such network structure, the dynamic aggregation object with hybrid cross-linked structure contains covalently to be handed over there are two common It networks network, contains the covalently inorganic boric acid estersil key crosslinking of common covalent cross-linking and dynamic in wherein at least one network simultaneously；Its In, at least one common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous heterochain structure；The dynamic is total Any one B atom connect to form three B-O-Si keys with three-O- in the inorganic boric acid estersil key of valence, and at least partly at least The linker of different Si atoms connection in two different B-O-Si keys based on different B atoms is linker L, the linker Contain the carbon atom on dynamic covalent polymer main chain backbone in L；
In another kind network structure therein, the dynamic aggregation object with hybrid cross-linked structure is containing there are two common covalent Cross-linked network, and wherein it is dispersed with the noncrosslinking dynamic covalent polymer containing the covalent inorganic borate key of dynamic；Wherein, At least one common covalent cross-linking network skeleton is polysiloxanes chain structure or siliceous heterochain structure；The covalent nothing of dynamic Any one B atom is connect with three-O- in machine boric acid estersil key, and at least partly from least two based on different B atoms The linker of different Si atoms connection in different B-O-Si keys is to contain in dynamic covalently in linker L, the linker L Carbon atom on main polymer chain skeleton；
In another kind network structure therein, the dynamic aggregation object with hybrid cross-linked structure is containing there are two common covalent Cross-linked network, and be wherein dispersed with the covalent inorganic crosslinked dynamic covalent polymer particle of borate key of dynamic；Wherein, institute It is polysiloxanes chain structure or siliceous heterochain structure to state common covalent cross-linking network skeleton；The covalent inorganic boric acid estersil of the dynamic Any one B atom is connect with three-O- in key, and at least partly from at least two different B-O-Si based on different B atoms The linker of different Si atoms connection in key is in linker L, the linker L containing in dynamic covalent polymer main chain Carbon atom on skeleton；
In another kind network structure therein, the dynamic aggregation object with hybrid cross-linked structure contains there are three network, In two be common covalent cross-linking network；It is formed with the covalent inorganic boric acid estersil key of dynamic wherein in dynamic covalent cross-linking network Crosslinking reaches its gel point or more, and without common covalent cross-linking more than gel point；Wherein, at least one described common covalent Cross-linked network skeleton is polysiloxanes chain structure or siliceous heterochain structure；The dynamic is covalently any one in inorganic boric acid estersil key A B atoms are connect with three-O-, and wherein at least part from at least two different B-O-Si keys based on different B atoms The linker of different Si atoms connections is in linker L, the linker L containing on dynamic covalent polymer main chain backbone Carbon atom.
11. the dynamic aggregation object according to claim 9 with hybrid cross-linked structure, which is characterized in that described has The dynamic aggregation object of hybrid cross-linked structure contains one or more kinds of hydrogen bond groups, is present in cross-linked polymer cross-linked network In network chain backbone or in non-cross-linked polymer main chain backbone, or exist simultaneously in cross-linked polymer cross-linked network chain backbone and Fei Jiao In linked polymer main chain backbone.
12. the dynamic aggregation object according to claim 11 with hybrid cross-linked structure, which is characterized in that described has The hydrogen bond group that the dynamic aggregation object of hybrid cross-linked structure contains contains at least one of following constituent：
13. the dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-12, which is characterized in that The dynamic aggregation object with hybrid cross-linked structure is with following any character：Ordinary solid, elastomer, gel, bubble Foam.
14. the dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-12, which is characterized in that The raw material components for being used to prepare the dynamic aggregation object further include it is following any or appoint it is several can additive or usable object：Its His polymer, 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.
15. the dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-12, which is characterized in that The dynamic aggregation object is applied to following material or product：Damping shock absorber, speed lockup's device, antidetonation shear plate, cycle are answered Power carrying tool, defense of resistance to impact material, athletic protective article, army and police's protective article, shape-memory material, is answered at padded coaming Power sensitive material, toy, body-building material, force snesor, binder, squeegee, bulletproof glass squeegee, block glue, casting glue, Scratch resistant coatings, toughness material, tough elastomer material, self-repairability coating, self-repairability film, self-repairability plank, from Prosthetic binder, self-repairability sealing material, self-repairability toughness material.
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