CN109666130A - A kind of energy-absorbing method based on dynamic aggregation object - Google Patents

A kind of energy-absorbing method based on dynamic aggregation object Download PDF

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CN109666130A
CN109666130A CN201710966080.XA CN201710966080A CN109666130A CN 109666130 A CN109666130 A CN 109666130A CN 201710966080 A CN201710966080 A CN 201710966080A CN 109666130 A CN109666130 A CN 109666130A
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dynamic
linking
cross
aggregation object
group
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不公告发明人
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Weng Qiumei
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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    • C08G18/3829—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing ureum groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a kind of energy-absorbing methods based on dynamic aggregation object, a kind of dynamic aggregation object and the progress energy-absorbing using it as energy-absorbing material are provided, contain the commutative covalent bond based on alkyl triazole in the dynamic aggregation object simultaneously and the halogenated alkyl reacted can be swapped with alkyl triazole, and contains at least one cross-linked network.In the dynamic aggregation object, the dynamic of dynamic aggregation object selectively also is further enhanced containing the hydrogen bond group that can form supermolecule hydrogen bond action.The dynamic aggregation object object is used as energy-absorbing material can provide the functions such as good shock resistance (protection), damping, damping, buffering, sound insulation, noise elimination, simultaneously with optional supermolecule hydrogen bond collective effect, the characteristics such as material stimulating responsive, self-repairability, recuperability, repeatable processability are assigned, can be applied to the various aspects of daily life Yu each professional domain.

Description

A kind of energy-absorbing method based on dynamic aggregation object
Technical field
The present invention relates to a kind of energy-absorbing methods, and in particular to a kind of energy-absorbing method based on dynamic aggregation object.
Background technique
In the activity such as daily life, movement, amusement and recreation, military affairs, police service, security, medical care, production, human body, animal body Seriously affecting for the physical impacts such as shock, vibration, vibration, explosion, sound is often subject to article etc..By using energy-absorbing material Energy-absorbing is carried out, effective protection can be played to this kind of physical impact, is alleviated, to reach such as shock resistance, damping, damping, delay Punching, sound insulation, noise elimination and other effects.At this stage, mainly there are metal, polymer, composite material etc. for the material of energy-absorbing.It is a kind of common Polymer material energy-absorbing mechanism be cracked using the fracture and material internal of the chemical bonds such as covalent bond even material The processes energy-absorbings such as whole fracture.However during above-mentioned each, fracture and the crackle of macroscopic view, the fracture of covalent bond are once generated Can not often it restore, the energy absorption ability and mechanical property that will lead to material are all reduced or even can not be continued to use, primary or few For number several times after endergonic process, material must be replaced in time could maintain original performance.
Therefore, it is necessary to develop the new energy-absorbing method of one kind can both embody excellent suction on the basis of the energy-absorbing mechanism Can effect, and can to avoid material because energy-absorbing be broken due to global failure, to solve problems of the prior art.
Summary of the invention
For above-mentioned background, in order to make polymer material that can not only embody excellent energy-absorbing effect, but also can be to avoid material Global failure due to energy-absorbing fracture, the present invention provides a kind of energy-absorbing methods based on dynamic aggregation object.For this purpose, we are polymerizeing Dynamic covalent bond is introduced in object, replaces traditional chemical covalent to be crosslinked with dynamic covalent cross-linking.Dynamic covalent cross-linking can be in material Selfreparing is carried out to material after being broken, not only maintains the structure and mechanical property of polymer, and prior is to confer to Polymer can be repeated as many times the ability of energy-absorbing.Optional supermolecule hydrogen bond crosslinks, reversible breaking property is not still to energy-absorbing The enhancing of effect can also further increase crosslink density, the stability and mechanical property of reinforcing material；Meanwhile supermolecule hydrogen Key provides dynamic, and the self-repairability of polymer also can be enhanced.
The present invention is achieved by following technical solution:
A kind of energy-absorbing method based on dynamic aggregation object, which is characterized in that provide a kind of dynamic aggregation object and using its as Energy-absorbing material carries out energy-absorbing, wherein containing at least one cross-linked network in the dynamic aggregation object, and simultaneously containing based on alkane The commutative covalent bond of base triazole and the halogenated alkyl reacted can be swapped with alkyl triazole；Wherein, it is described based on The commutative covalent bond of alkyl triazole has structure shown in following formula formula (1):
Wherein, X—For anion, it is selected from bromide ion, iodide ion；Expression and polymer chain are any other suitable The connection of group/atom；
Wherein, described to swap the halogenated alkyl reacted with the commutative covalent bond based on alkyl triazole and have Structure shown in following formula formula (2):
Wherein, X is halogen atom, is selected from bromine atom, iodine atom；Wherein,It indicates and polymer chain or any other The connection of suitable group or atom.
In one embodiment of the invention, wherein at least one glass transition temperature of the dynamic aggregation object Not higher than 25 DEG C.
In one embodiment of the invention, wherein at least one glass transition temperature of the dynamic aggregation object Not higher than 0 DEG C.
In one embodiment of the invention, wherein all glass transition temperature of the dynamic aggregation object not Higher than 25 DEG C.
In one embodiment of the invention, wherein all glass transition temperature of the dynamic aggregation object not Higher than 0 DEG C.
In one embodiment of the invention, wherein at least one glass transition temperature of the dynamic aggregation object Higher than 25 DEG C and it is lower than 40 DEG C.
In one embodiment of the invention, wherein at least one glass transition temperature of the dynamic aggregation object Dissociation temperature not less than 40 DEG C and not higher than dynamic covalent bond.
In one embodiment of the invention, wherein all glass transition temperature of the dynamic aggregation object not Dissociation temperature lower than 40 DEG C and not higher than dynamic covalent bond.
In one embodiment of the invention, wherein the dynamic aggregation object also contains at least one and can form oversubscription The hydrogen bond group of sub- hydrogen bond action.
In one embodiment of the invention, wherein only one cross-linked network, friendship in the dynamic aggregation object Only contain dynamic covalent cross-linking in networking network, the degree of cross linking reaches its gel point or more.
In one embodiment of the invention, wherein only one cross-linked network, friendship in the dynamic aggregation object It is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in networking network, wherein the degree of cross linking of dynamic covalent cross-linking reaches its gel Or more, the degree of cross linking of supermolecule crosslinking is in its gel point above and below.
In one embodiment of the invention, wherein only one cross-linked network, friendship in the dynamic aggregation object It is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in networking network, wherein the degree of cross linking of dynamic covalent cross-linking is in its gel point Hereinafter, the degree of cross linking of supermolecule crosslinking is more than its gel point.
In one embodiment of the invention, wherein only one cross-linked network, friendship in the dynamic aggregation object It is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in networking network, wherein the degree of cross linking of dynamic covalent cross-linking is in its gel point Hereinafter, supermolecule crosslinking the degree of cross linking in its gel point hereinafter, but the sum of the two degree of cross linking more than gel point.
In one embodiment of the invention, wherein containing there are two networks in the dynamic aggregation object；In 1st network Dynamic covalent cross-linking is contained only, the degree of cross linking is more than its gel point；Supermolecule crosslinking is contained only in 2nd network, the degree of cross linking is at it It is more than gel point.
In one embodiment of the invention, wherein containing there are two networks in the dynamic aggregation object；In 1st network Covalent cross-linking containing dynamic and supermolecule are crosslinked, and are crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein The degree of cross linking of dynamic covalent cross-linking is more than its gel point, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below；2nd Supermolecule crosslinking is contained only in network, the degree of cross linking is more than its gel point.
In one embodiment of the invention, wherein containing a network in the dynamic aggregation object, wherein containing only There is the dynamic covalent cross-linking of gel point or more, the supermolecule degree of cross linking is dispersed in dynamic in its gel point supermolecule polymer below In covalent cross-linking network.
In one embodiment of the invention, wherein containing a network, the cross-linked network in the dynamic aggregation object Be crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in network, wherein the degree of cross linking of dynamic covalent cross-linking reach its gel point with On, the degree of cross linking of supermolecule crosslinking is in its gel point above and below；The supermolecule degree of cross linking is in its gel point supermolecule below Polymer is dispersed in dynamic covalent cross-linking network.
In one embodiment of the invention, wherein containing a network in the dynamic aggregation object, wherein containing only There is the dynamic covalent cross-linking of gel point or more, supermolecule polymer of the supermolecule degree of cross linking more than its gel point is with graininess It is dispersed in dynamic covalent cross-linking network.
In one embodiment of the invention, wherein containing a network, the cross-linked network in the dynamic aggregation object Be crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in network, wherein the degree of cross linking of dynamic covalent cross-linking reach its gel point with On, the degree of cross linking of supermolecule crosslinking is in its gel point above and below；Supermolecule of the supermolecule degree of cross linking more than its gel point Polymer is dispersed in dynamic covalent cross-linking network with graininess.
In one embodiment of the invention, wherein at least a kind of hydrogen bond group is located at institute in the hydrogen bond group The side group or side chain or side group and side chain for the dynamic aggregation object stated.
In one embodiment of the invention, wherein at least a kind of hydrogen bond group contains simultaneously in the hydrogen bond group Have hydrogen bond donor and hydrogen bond receptor, wherein the hydrogen bond group for containing hydrogen bond donor and hydrogen bond receptor while described preferably comprise to A few secondary amino group, at least one of further preferably following constituent:
Wherein,Indicate the connection with polymer chain or any other suitable group/atom (including hydrogen atom),WithBetween can be cyclic or not cyclic.
In one embodiment of the invention, the hydrogen bond group is selected from carbamate groups, urea groups, sulfo-amino Formic acid ester group and the derivative of the above group etc..
In one embodiment of the invention, wherein the dynamic aggregation object contains at least one four teeth that are no more than Hydrogen bond group.
In one embodiment of the invention, wherein the dynamic aggregation object contains two or more hydrogen bond base Group.
In one embodiment of the invention, the wherein X in formula (1)—For bromide ion；Wherein the X in formula (2) is that bromine is former Son.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that main chain is carbon-chain structure or carbon heterochain The polymer segment of structure.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that main chain is the poly- of element heterochain structure Polymer segments.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that glass transition temperature is not higher than 25 DEG C polymer segment.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that glass transition temperature is not higher than 0 DEG C polymer segment.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that glass transition temperature is higher than 25 DEG C And the polymer segment lower than 40 DEG C.
In one embodiment of the invention, wherein for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalently At least one of polymer segment of key and hydrogen bond group, hydrogen bond group and hydrogen bond group is that glass transition temperature is not less than 40 DEG C and lower than dynamic covalent bond dissociation temperature polymer segment.
In one embodiment of the invention, wherein the dynamic aggregation object has following any character: common solid Body, elastomer, gel, foam.
In one embodiment of the invention, it further includes following for constituting the recipe ingredient of the wherein described dynamic aggregation object It is any or appoint it is several can additive or usable object: other polymers, auxiliary agent, filler, sweller.Wherein, other described Polymer preferably is selected from following any or appoints several: natural polymer, synthetic macromolecular compound；The auxiliary agent is excellent Selected from it is following any or appoint it is several: catalyst, initiator, antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsification Agent, fire retardant, toughener, coupling agent, solvent, lubricant, release agent, plasticizer, thickener, thixotropic agent, levelling agent, coloring Agent, fluorescent whitening agent, delustering agent, antistatic agent, dehydrating agent, biocide mildewcide, foaming agent, blowing promotor, nucleating agent, rheology Agent；The filler preferably is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler；Described Sweller preferably is selected from following any or appoints several: water, organic solvent, ionic liquid, oligomer, plasticizer.
In one embodiment of the invention, the energy-absorbing method is applied to defense of resistance to impact, damping, damping, delays Punching, explosion-proof, shellproof, sound insulation, noise elimination.
Compared with prior art, the invention has the following advantages:
(1) in the energy-absorbing method provided by the invention based on dynamic aggregation compositions, when dynamic aggregation object is in energy-absorbing Using when by external force and inside cracks or after being broken, can be with using the dynamic of dynamic covalent bond and optional hydrogen bond It realizes material self-repairability, without replacement, use can be continued cycling through, can satisfy the environmental protection growing to new material Demand, this cannot achieve in the existing method for carrying out energy-absorbing with polymeric system.
(2) in the energy-absorbing method provided by the invention based on dynamic aggregation object, used dynamic covalent bond is based on alkane Base triazole, raw material are easy to get, and it is simple easy to synthesize, and are suitble to industrialization.The exchange reaction of itself and halogenated alkyl does not need to be catalyzed Agent only need to be heated and can be carried out, and the exchange rate of exchange reaction can be regulated and controled by heating temperature.Therefore, it can satisfy Widest energy-absorbing requirement.
(3) in the assembly energy-absorbing method provided by the invention based on dynamic aggregation object, also selectively there is supermolecule Hydrogen bond action.When polymer is by external impacts, strain-responsive can occur for dynamic supermolecule hydrogen bond, on molecular scale Degree of cross linking transient state increases, so that flexible and rigid transition occur, can impact energy effectively dispersed；And work as polymer When the external impacts being subject to are sufficiently large, supermolecule hydrogen bond action, can be in stress due to dynamic and weaker bond energy It can be dissociated under impact condition with key-shaped formula can be sacrificed, expand the range to energy absorption, further enrich dynamic The energy-absorbing mechanism of polymer, has expanded the application range of energy-absorbing method.
(4) energy-absorbing method provided by the invention based on dynamic aggregation object has good Modulatory character.For example, by oversubscription Sub- hydrogen bond and dynamic covalent bond combine, and by parameters such as molecular structure, the molecular weight of control raw material, can prepare has difference The adjustable dynamic aggregation object of appearance features, performance is used for energy-absorbing；For another example, by controlling position, type and the number of hydrogen bond group, Dynamic reversibility dynamic aggregation object of different strengths and weaknesses can be prepared, is dissociated under different stress conditions, realizes multiple suction The effect of energy.By controlling the ratio of both dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks ingredient, make the supermolecule hydrogen Key crosslinking both can form cross-linked network in the same network jointly with dynamic covalent cross-linking, can also be individually formed supermolecule Dynamic crosslinking network can also be individually formed the particle of supermolecule dynamic crosslinking, can also be with noncrosslinking supermolecule polymer Form be dispersed in dynamic covalent cross-linking network or supermolecule crosslinking with dynamic covalent cross-linking is respectively formed interpenetrating or Semi-IPN Two networks etc., different structures can achieve different energy-absorbing effects.In addition, when two networks all contain supermolecule crosslinking When, the supermolecule crosslinking that can use in two networks provides collaboration or orthogonal dynamic to adjust energy-absorbing range.
(5) compared to other existing energy-absorbing methods, the present invention is also fully utilized by dynamic covalently in addition to energy absorption performance Other characteristics of key, optional supermolecule hydrogen bond and polymer can provide mechanical strength, self-repairability, shape memory, multiple Other diversified performances such as responsiveness.In addition, other function can also be added according to actual needs in material preparation process Property additive is modified dynamic aggregation object, has further expanded the performance and energy-absorbing application range of material.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific embodiment
The present invention relates to a kind of energy-absorbing methods, which is characterized in that provides a kind of dynamic aggregation object and using it as energy-absorbing material Material carries out energy-absorbing, wherein in the dynamic aggregation object simultaneously containing based on alkyl triazole commutative covalent bond and can be with alkane Base triazole swaps the halogenated alkyl of reaction, and contains at least one cross-linked network.
Term " energy-absorbing " used refers to for caused by the forms such as shock, vibration, vibration, explosion, sound in the present invention Physical impact absorption, dissipation and the dispersion of the energy that generate, but do not include the only absorption to thermal energy and/or electric energy, to reach To such as shock resistance (protection), damping, damping, buffering, sound insulation, noise elimination and other effects.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention It may include the option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
Heretofore described " polymerization " reaction/action be chain propagation process/effect, namely by intermolecular reaction/ Effect (including covalent chemical reaction and supermolecule hydrogen bond action) formation straight chain, branching, ring, two-dimensional/three-dimensional cluster, three-dimensional are unlimited The polymer of network structure.
Term " crosslinking " reaction/action used in the present invention, refer to intermolecular and/or intramolecular by covalent bond and/ Or supermolecule hydrogen bond action forms the process with three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is generally first Constantly increase in two-dimensional/three-dimensional direction, gradually form cluster (can be two dimension or three-dimensional), developing deeply is three-dimensional infinite net Network.Therefore, crosslinking can be considered as a kind of special shape of polymerization.In cross-linking process, just reach a three-dimensional infinite network When the degree of cross linking, referred to as gel point, also referred to as percolation threshold.The cross-linking products (contained, similarly hereinafter) more than gel point, have Three-dimensional infinite network structure, cross-linked network constitute an entirety and across entire polymer architectures；In gel point friendship below Co-product, is only lax interchain link structure, and not formed three-dimensional infinite network structure, and is not belonging to across entire polymerization The cross-linked network that can constitute an entirety of object structure.Unless stated otherwise, the present invention in cross-linked structure be gel point with On three-dimensional infinite network structure, non-crosslinking structure includes the line style that the degree of cross linking is zero and non-linearity structure and gel point or less Two-dimensional/three-dimensional cluster structure.
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 any segment being present in cross-linked network skeleton.It is described 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 main polymer chain phase Connect and be distributed in the chain structure of main chain side；Wherein, " branch "/" bifurcated chain " can be side chain and be also possible to other The chain structure come out from any chain bifurcated.Wherein, " side group " refers to that any chain of same polymer is connected and is distributed in The chemical group of chain side.Wherein, " end group " refers to that any chain of same polymer is connected and is located at the change of chain end Learn group.If not otherwise indicated, side group refers in particular to group of the molecular weight no more than 1000Da for being connected to polymer chain skeleton side And subunit group therein.When the molecular weight of side chain, branch, bifurcated chain is no more than 1000Da, itself and group thereon are regarded For side group.For the sake of simplicity, if not otherwise indicated, side chain, branch, bifurcated chain are collectively referred to as side chain.Above-mentioned " side chain ", " side Base " can have multilevel structure namely side chain/side group that can continue with side chain/side group, side chain/side group side chain/side group It can continue have side chain/side group.In the present invention, if not otherwise indicated, for hyperbranched and dendroid chain and its relevant link Structure, the polymer segment of outermost can be considered as side chain, and rest part can be considered as main chain.
Heretofore described " dynamic covalent cross-linking network " is referred to when supermolecular mechanism is all disconnected in covalent cross-linking network It opens when only remaining common covalent bond and dynamic covalent bond, still with the polymer network of the above structure of gel point；And when dynamic is total When valence link also all disconnects, original crosslinked polymer network dissociation resolves into following any or appoints several secondary units: monomer gathers Close object chain segment, polymer cluster, polymer beads more than gel point etc..
Heretofore described " supermolecule cross-linked network " refers to all disconnecting only when the dynamic covalent bond in cross-linked network When remaining common covalent bond and supermolecule hydrogen bond, still with the polymer network of the above structure of gel point；And work as supermolecule hydrogen bond When also all disconnecting, following any or several secondary units: monomer, polymer are resolved into original crosslinked polymer network dissociation Chain segment, polymer cluster, polymer beads more than gel point etc..
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key, under typical temperature (is generally not more than 100 DEG C) and (generally less than 1 day) is more difficult in the usual time is broken 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..
Heretofore described " dynamic covalent bond " refers to can swap under certain condition instead based on alkyl triazole The commutative covalent bond answered.Wherein, described " exchange reaction " refers to, new covalent bond is generated and solved with old covalent bond From to generate the exchange of chain and the variation of polymer topological structure.For the purpose of the present invention, in this exchange process, due to handing over The particularity of reaction is changed, the crosslink density of polymer network is basically unchanged.Wherein, described " certain condition " refer to can with can hand over Alkyl triazole is changed to swap in the presence of the halogenated alkyl and solvent of reaction and suitable temperature, humidity, pressure condition etc..
Heretofore described " supermolecular mechanism " refers to supermolecule hydrogen bond action, referred to as " hydrogen bond action " or " hydrogen bond ".
In embodiments of the present invention, the dynamic aggregation object can not have glass transition temperature, can have There is one or more glass transition temperature.Wherein, a kind of preferred embodiment is the dynamic aggregation object At least one glass transition temperature is not higher than 25 DEG C, more preferably not above 0 DEG C, more preferably when there are multiple glass transition temperatures The glass transition temperature of Shi Suoyou is not higher than 25 DEG C, and most preferably all glass transition temperatures are not higher than 0 DEG C, helps to embody super Dynamic and self-repairability of the molecule hydrogen bond when room temperature and low temperature use, the materials such as readily available adhesive, elastomer, gel Or product；Another preferred embodiment is that at least one glass transition temperature of the dynamic aggregation object is higher than 25 DEG C But it is lower than 40 DEG C, help to obtain that size is relatively stable, dynamic is moderate, the higher elastomer of temperature sensitivity, foam and general Logical solid etc.；At least one vitrifying that another preferred embodiment is the dynamic aggregation compositions component A turns Dissociation temperature (about 98 DEG C) of the temperature not less than 40 DEG C and lower than dynamic covalent bond, preferably all of glass transition temperature is not low Dissociation temperature in 40 DEG C and lower than dynamic covalent bond helps to embody material at high temperature dimensional stability, shape memory, low temperature With the characteristics such as hardness under room temperature, materials or the products such as the readily available gel with property, foam, ordinary solid.
In embodiments of the present invention, cross-linked network included in the dynamic aggregation object at least one, both It can be single one network, can also there is the multiple networks being mutually blended, can also there is multiple networks of interpenetrating, it can also be same When exist and be blended and interpenetrating, etc.；It can using any appropriate crosslinking topological structure, chemical structure, reactive mode and its Combination etc..
In embodiments of the present invention, the type of the commutative covalent bond based on alkyl triazole is not special Limitation, where position be also not particularly limited, the preferably at least partial dynamic covalent bond chain that is located at polymer network Skeleton could embody its dynamic；The commutative covalent bond based on alkyl triazole has to be tied shown in following formula formula (1) Structure:
Wherein, X-For anion, it is selected from bromide ion, iodide ion, preferably bromide ion.Indicate with polymer chain or The connection of any other suitable group/atom (including hydrogen atom).It is such when what is hereinafter occurred againIt all continues to use above-mentioned Definition and range, such as without special case, no longer progress repeated explanation.
In embodiments of the present invention, described to be swapped instead with the commutative covalent bond based on alkyl triazole The halogenated alkyl answered, where position be not particularly limited, can reside in end any appropriate in dynamic aggregation object In base, side group and/or side chain, or exist in any appropriate form in the other compositions such as small molecule, oligomer；Described can The halogenated alkyl reacted is swapped with the commutative covalent bond based on alkyl triazole has structure shown in following formula formula (2):
Wherein, X is halogen atom, is selected from bromine atom, iodine atom, preferably bromine atom.
In embodiments of the present invention, supermolecule hydrogen bond action can be formed by also selectively containing in dynamic aggregation object Hydrogen bond group.When including simultaneously supermolecule hydrogen bond action in dynamic aggregation object, network structure is more rich and varied, energy-absorbing effect Fruit is more preferably.When in dynamic aggregation object simultaneously include supermolecule hydrogen bond action when and included cross-linked network quantity be two or more When a, these networks can be identical or different；Can be subnetwork only includes that dynamic covalent cross-linking and subnetwork only wrap Containing supermolecule crosslinking combination, or part only include dynamic covalent cross-linking and part simultaneously comprising dynamic covalent cross-linking with The combination of supermolecule crosslinking, or part only include dynamic covalent cross-linking and supermolecule comprising supermolecule crosslinking and part simultaneously It all simultaneously include dynamic covalent cross-linking and supermolecule crosslinking in the combination of crosslinking or each network, but the present invention is not only It is limited to this.
(the first network structure) in a preferred embodiment of the present invention, only one in the dynamic aggregation object A cross-linked network, dynamic covalent cross-linking is only contained in the cross-linked network, and the degree of cross linking reaches its gel point or more.The network structure Structure is simple, and dynamic covalent cross-linking can keep balanced structure, and provides covalent dynamic under given conditions.
(second of network structure) in a preferred embodiment of the present invention, only one in the dynamic aggregation object A cross-linked network is crosslinked containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein the friendship of dynamic covalent cross-linking simultaneously Connection degree reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below.The network structure structure letter It is single, balanced structure can be kept by dynamic covalent cross-linking, supermolecule crosslinking provides dynamic；Under given conditions, dynamic Covalent cross-linking also can provide covalent dynamic.
In another preferred embodiment of the invention (the third network structure), in the dynamic aggregation object only There is a cross-linked network, is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein dynamic covalent cross-linking The degree of cross linking in its gel point hereinafter, supermolecule crosslinking the degree of cross linking more than its gel point.The network structure has good Dynamic is based particularly on the strain-responsive of supermolecule crosslinking；Dynamic covalent cross-linking not directly keep balanced structure, but Under the conditions of specific, dynamic covalent cross-linking also can provide additional covalent dynamic and play the role of regulation performance.
In another preferred embodiment of the invention (the 4th kind of network structure), in the dynamic aggregation object only There is a cross-linked network, is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein dynamic covalent cross-linking The degree of cross linking in its gel point hereinafter, the degree of cross linking of supermolecule crosslinking in its gel point hereinafter, but the sum of the two degree of cross linking solidifying It is more than glue point.Dynamic covalent cross-linking and the degree of cross linking of supermolecule crosslinking are lower in the network structure, and the whole of network structure is handed over Connection degree is not high, and dynamic covalent cross-linking and supermolecule crosslinking are most important to the effect for providing balanced structure regulation performance.
In another preferred embodiment of the present invention (the 5th kind of network structure), contain in the dynamic aggregation object Two networks；Dynamic covalent cross-linking is contained only in 1st network, the degree of cross linking is more than its gel point；Supermolecule is contained only in 2nd network Crosslinking, the degree of cross linking is more than its gel point.In the network structure, the 2nd network has good dynamic, and the 1st network provides Balanced structure can preferably play comprehensive effectiveness by the interpenetrating of two networks or the combinations such as Semi-IPN；Specific Under the conditions of, dynamic covalent cross-linking also can provide additional covalent dynamic and play the role of regulation performance.
In another preferred embodiment of the present invention (the 6th kind of network structure), contain in the dynamic aggregation object Two networks；Covalent cross-linking containing dynamic and supermolecule are crosslinked in 1st network, contain dynamic covalent cross-linking in the cross-linked network simultaneously It is crosslinked with supermolecule, wherein for the degree of cross linking of dynamic covalent cross-linking more than its gel point, the degree of cross linking of supermolecule crosslinking is solidifying at it Glue point above and below；Supermolecule covalent cross-linking is contained only in 2nd network, the degree of cross linking is more than its gel point.The network structure In, by combinations such as the interpenetrating of two networks, it can preferably play comprehensive effectiveness；And it can be using in two networks Supermolecule crosslinking provide collaboration or orthogonal dynamic.
In another preferred embodiment of the present invention (the 7th kind of network structure), contain in the dynamic aggregation object One network, wherein the supermolecule degree of cross linking is in its gel point oversubscription below only containing dynamic covalent cross-linking more than gel point Sub- polymer is dispersed in dynamic covalent cross-linking network.In the network structure, dynamic covalent cross-linking can keep balanced structure, Under the conditions of specific, dynamic covalent cross-linking also can provide covalent dynamic；Supermolecule polymer dispersed therein provides dynamic Property, especially strain-responsive.
In another preferred embodiment of the present invention (the 8th kind of network structure), contain in the dynamic aggregation object One network is crosslinked containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein the crosslinking of dynamic covalent cross-linking simultaneously Degree reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below；The supermolecule degree of cross linking is solidifying at it Glue point supermolecule polymer below is dispersed in dynamic covalent cross-linking network.In the network structure, dynamic covalent cross-linking can be with Balanced structure is kept, under given conditions, dynamic covalent cross-linking also can provide covalent dynamic；Supermolecule crosslinking provides dynamic Property, supermolecule polymer dispersed therein provides supplement dynamic, especially strain-responsive.
In another preferred embodiment of the present invention (the 9th kind of network structure), contain in the dynamic aggregation object One network, wherein only containing dynamic covalent cross-linking more than gel point, oversubscription of the supermolecule degree of cross linking more than its gel point Sub- polymer is dispersed in dynamic covalent cross-linking network with graininess.In the network structure, dynamic covalent cross-linking can be kept Balanced structure, under given conditions, dynamic covalent cross-linking also can provide covalent dynamic；The offer of supermolecule polymer particle is filled out It fills and dynamic, local viscosity and intensity can be obtained in strain-responsive and is increased.
In another preferred embodiment of the present invention (the tenth kind of network structure), contain in the dynamic aggregation object One network is crosslinked containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein the crosslinking of dynamic covalent cross-linking simultaneously Degree reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below；The supermolecule degree of cross linking is solidifying at it Supermolecule polymer more than glue point is dispersed in dynamic covalent cross-linking network with graininess.In the network structure, dynamic is altogether Valence crosslinking can keep balanced structure, and under given conditions, dynamic covalent cross-linking also can provide covalent dynamic；Supermolecule is handed over Connection provides dynamic, and supermolecule polymer particle provides filling and supplement dynamic, and part can be obtained in strain-responsive Viscosity and intensity increase.
In the present invention, there can also be other diversified embodiments.Those skilled in the art can be according to this The logic and train of thought of invention, are rationally and effectively realized.
In the present invention, the hydrogen bond group that hydrogen bond action can be formed existing for the selectivity includes being present in polymer Hydrogen bond group (calling " skeleton hydrogen bond group " in the following text) and place on chain backbone (including on main chain/side chain/branch/bifurcated chain backbone) In in polymer chain side group hydrogen bond group (calling " side group hydrogen bond group " in the following text) and polymer chain and other compound ends Hydrogen bond group (calls " end group hydrogen bond group " in the following text).The skeleton hydrogen bond group refers to that at least one atom in the group is straight Connect and participate in the building polymer chain skeleton, including main polymer chain, side chain, branch, bifurcated chain skeleton；The side group Hydrogen bond group refers to all atoms on the group in polymer chain side group；The end group hydrogen bond group, such as non-specifically Illustrate, refers to all atoms on the group in polymer chain end.
In embodiments of the present invention, hydrogen bond group existing for the selectivity can be with skeleton hydrogen bond group, side The combination of any one or more of the forms such as base hydrogen bond group, end group hydrogen bond group is present in the dynamic aggregation object. It can be formed between the hydrogen bond group of different location under specific circumstances since part hydrogen bond does not have directionality and selectivity Hydrogen bond action, can be mutual between the hydrogen bond group of identical or different position in identical or different polymer molecule Hydrogen bond action is formed, it can also be with the institutes such as example optional other polymers molecule of the other compositions in polymer, filler, small molecule Hydrogen bond action is formed between the hydrogen bond group contained.As an example, the hydrogen bond action in the present invention includes but is not limited to such as: described Hydrogen bond group in side chain and/or side group forms interchain hydrogen bond crosslinking between different molecular；Hydrogen in the side chain and/or side group Interchain hydrogen bond crosslinking is formed in key group and the main chain backbone between hydrogen bond group；In the part side chain and/or side group Chain inner ring is independently formed with hydrogen bond between hydrogen bond group；Independently with hydrogen bond between hydrogen bond group in the main chain backbone of part Form chain inner ring；Hydrogen bond group collective effect in the part side chain and/or side group forms chain inner ring etc. with hydrogen bond.It needs to refer to Out, it is not excluded for part in the present invention and is formed by intrachain hydrogen bond effect neither formation inter-chain action, does not also form chain inner ring, Only form the effects of including but are not limited to grafting.
In embodiments of the present invention, the position of hydrogen bond group does not have any restriction, can be any appropriate position. In the preferred embodiment of the present invention, pendant hydrogen key group is only contained in the dynamic aggregation object；Of the invention another In a kind of preferred embodiment, main chain backbone hydrogen bond group is only contained in the dynamic aggregation object；It is excellent in another kind of the invention It selects in embodiment, side chain skeleton hydrogen bond group is only contained in the dynamic aggregation object；It is preferably implemented in another kind of the invention In mode, side chain end group hydrogen bond group is only contained in the dynamic aggregation object；In another preferred embodiment of the invention, Only contain main chain end group hydrogen bond group in the dynamic aggregation object；It is described dynamic in another preferred embodiment of the invention Only contain pendant hydrogen key group and side chain skeleton hydrogen bond group in state polymer；In another preferred embodiment of the invention In, pendant hydrogen key group and main chain backbone hydrogen bond group are only contained in the dynamic aggregation object；It is preferred in another kind of the invention In embodiment, pendant hydrogen key group and main chain end group hydrogen bond group are only contained in the dynamic aggregation object；Of the invention another In a kind of preferred embodiment, pendant hydrogen key group and side chain end group hydrogen bond group are only contained in the dynamic aggregation object；At this In another preferred embodiment of invention, side chain end group hydrogen bond group and main chain backbone hydrogen are only contained in the dynamic aggregation object Key group；In another preferred embodiment of the invention, side chain end group hydrogen bond group is only contained in the dynamic aggregation object With main chain end group hydrogen bond group；In another preferred embodiment of the invention, only contain main chain in the dynamic aggregation object End group hydrogen bond group and main chain backbone hydrogen bond group；In another preferred embodiment of the invention, the dynamic aggregation object In only contain pendant hydrogen key group, side chain end group hydrogen bond group and main chain backbone hydrogen bond group；It is preferred in another kind of the invention In embodiment, pendant hydrogen key group, side chain end group hydrogen bond group and main chain end group hydrogen bond are only contained in the dynamic aggregation object Group；In another preferred embodiment of the invention, pendant hydrogen key group, side chain end are only contained in the dynamic aggregation object Base hydrogen bond group and side chain skeleton hydrogen bond group；In another preferred embodiment of the invention, in the dynamic aggregation object Only contain pendant hydrogen key group, side chain skeleton hydrogen bond group and main chain end group hydrogen bond group；It is preferred real in another kind of the invention It applies in mode, pendant hydrogen key group, side chain skeleton hydrogen bond group, side chain end group hydrogen bond group is only contained in the dynamic aggregation object With main chain backbone hydrogen bond group；In another preferred embodiment of the invention, only contain side group in the dynamic aggregation object Hydrogen bond group, side chain skeleton hydrogen bond group, side chain end group hydrogen bond group and main chain end group hydrogen bond group；In another kind of the invention In preferred embodiment, side group hydrogen bond group, side chain end group hydrogen bond group, side chain skeleton hydrogen bond are contained in the dynamic aggregation object Group, main chain end group hydrogen bond group and main chain backbone hydrogen bond group.But the present invention is not limited only to this.
In embodiments of the present invention, since the general quantity of main chain backbone hydrogen bond group is than relatively limited and not easy to control, And the side chain/side group hydrogen bond group can before polymerized/cross-linked, later or in the process generate, before or after generate Quantity can be than relatively freely controlling, and side chain/side group hydrogen bond freedom degree is higher is more prone to produce dynamic, side chain/ Link structure, length and the structure of itself between side group hydrogen bond group and skeletal chain include that substituent group and side group etc. can be into The diversified adjusting of row, therefore, it includes a kind of side chain/side group hydrogen bond base that the supermolecule hydrogen bond group in the present invention, which is preferably at least, Group, to control HYDROGEN BOND INTENSITY, steric hindrance, thermal stability, glass transition temperature etc., and then regulates and controls its dynamic property, assigns Give the performances such as the different ultra-tough of polymer, selfreparing, strain-responsive, shape memory.
In embodiments of the present invention, the hydrogen bond action in the supermolecular mechanism by hydrogen bond group donor (H, Namely hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) interaction formed, can be times The meaning number of teeth.Wherein, the number of teeth refers to being formed by hydrogen bond quantity, each H ... Y group by the donor and receptor of hydrogen bond group It is combined into a tooth.In following formula, the bonding situation of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bonds.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:
In embodiments of the present invention, the number of teeth of hydrogen bond is not limited.The number of teeth of hydrogen bond is more, and synergistic effect is got over Greatly, the intensity of hydrogen bond is bigger.If the number of teeth for being formed by hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is just It is weak, it can be used as structural hydrogen bond and play promotion dynamic aggregation object holding balanced structure and improve mechanical property (modulus and intensity) Effect.If the number of teeth of formed hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond action is with regard to strong.It is a kind of preferred in the present invention Embodiment for select be no more than four teeth hydrogen bond dynamic is provided；Another preferred embodiment is to select two kinds or two Kind or more hydrogen bond group form the different hydrogen bond of dynamic, multi-level dynamic is provided.
In embodiments of the present invention, the hydrogen bond action can be by existing between any appropriate hydrogen bond group Noncovalent interaction generates, and the hydrogen bond group can only contain hydrogen bond donor, or only contain hydrogen bond receptor, or contain simultaneously There are a hydrogen bond donor and receptor, preferably the hydrogen bond group simultaneously containing hydrogen bond donor and receptor is so that it can be separately formed hydrogen bond Effect, contain while described hydrogen bond donor and receptor hydrogen bond group its preferably comprise at least one secondary amino group with flowering structure at At least one of point:
Wherein,Indicate the connection with polymer chain or any other suitable group/atom (including hydrogen atom)；WithBetween can be cyclic or not cyclic.
Wherein, pass throughThe group or atom of connection are denoted as G.The structure of G is not particularly limited, and respectively independently includes But it is not limited to linear chain structure, the branched structure containing side group or cyclic structure.Wherein, cyclic structure is not particularly limited, and can be selected from Aliphatic ring, aromatic ring, saccharide ring, condensed ring, preferred aliphat ring.
The structure of G is respectively independently preferably linear chain structure.
G can contain hetero atom, can also be free of hetero atom.
The carbon atom number of G is not particularly limited, and respectively independent is preferably 1~20, and respective independent more preferably 1~10.
G is each independently selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substitution Miscellaneous alkyl.Wherein, the substitution atom in G or substituent group are not particularly limited, and are each independently selected from halogen atom, alkyl replaces Base contains heteroatomic substituent group.
G is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, aromatic hydrocarbons Base, C1-20Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Alkylthio acyl group and its any substituted form.
G is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20Rouge Miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20Alkyl sulfenyl acyl group, artyl sulfo acyl Base and its any substituted form.
G is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20Rouge Miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxy carbonyl, aryloxycarbonyl, C1-20Alkyl sulfenyl carbonyl, artyl sulfo carbonyl Base, C1-20Alkoxy carbonyl, aryloxy thiocarbonyl, C1-20Alkyl sulfenyl thiocarbonyl, artyl sulfo thiocarbonyl and Its any substituted form.
Specifically, G is each independently selected from including but not limited to hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, first Base, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ten Trialkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, Acrylic, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, benzyl Epoxide carbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzylaminocarbonyl, first Oxygroup thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, second sulphur Base thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, substituted C1-20Alkyl, substituted C1-20Alkenyl, replace Aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl alkyl, substituted C1-20Alkane Epoxide carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, substituted artyl sulfo carbonyl, replace C1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl sulfenyl thiocarbonyl, substituted virtue Base alkylthio carbonyl.Wherein, butyl includes but is not limited to normal-butyl, tert-butyl.Octyl includes but is not limited to n-octyl, 2- second Base hexyl.Wherein, atom or substituent group is replaced to be selected from halogen atom, hydrocarbyl substituent, contain heteroatomic substituent group.
It is preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, penta that G is further respectively independent Base, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, 16 Alkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, benzyl, trityl, phenyl, benzyl, methyl Benzyl, nitrobenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, acetyl group, benzoyl, 2- pyridylcarbonyl, Methoxycarbonyl, ethoxy carbonyl, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto carbonyl, ethylmercapto group Carbonyl, tert. butyl-sulphenyl carbonyl, thiophenyl carbonyl, benzylthio carbonyl, ethylenebis dithiocarbamate carbonyl, phenyl first thiocarbonyl, methoxyl group Thiocarbonyl, ethyoxyl thiocarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, first sulphur Base thiocarbonyl, ethylmercapto group thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, C1-10It halohydrocarbyl, trifluoroacetyl group, halogenophenyl, halogeno-benzyl, nitrobenzophenone, nitrobenzyl and its any is substituted Form.Wherein, replace atom or substituent group is preferably fluorine atom, alkoxy, nitro.
G respectively independent more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, triphen Methyl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, 2- pyridylcarbonyl, tert-butyl Epoxide carbonyl, phenyloxycarbonyl, benzyloxycarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, the thio carbonyl of benzyloxy Base, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group.
G is respectively independently more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, three Benzyl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio.
G is respectively independently most preferably hydrogen atom, methyl, ethyl, n-propyl, normal-butyl.
In another preferred embodiment of the invention, hydrogen bond group preferably is selected from carbamate groups, urea groups, thio Carbamate groups and the derivative of the above group etc., because of its abundant raw material, synthesis is simple, is suitble to industrialized production.
As an example, the hydrogen bond group in following side group and/or end group can be enumerated, but the present invention is not limited only to this.
Wherein, m, n, x are the quantity of recurring group, can be fixed value, are also possible to average value.M, n value range is 0 With the integer for being more than or equal to 1；X value range is the integer more than or equal to 1.
As an example, the hydrogen bond group on main chain and/or side chain skeleton as described below can be enumerated, but the present invention not only limits In this.
In embodiments of the present invention, the hydrogen bond group of hydrogen bond action is formed either mutual between different hydrogen bond groups Apotype combination is also possible to combining between hydrogen bond group of the same race from complementary type, makees as long as being capable of forming suitable hydrogen bond between group With.The combination of some hydrogen bond groups can be exemplified below, but the present invention is not limited only to this:
In the present invention, the supermolecule hydrogen bond action, which can be, carries out dynamic supermolecule crosslinking/poly- in dynamic aggregation object It is generated during conjunction；Dynamic supermolecule crosslinking/polymerization is carried out again after being also possible to pre-generated supermolecule hydrogen bond action；It can also After dynamic supermolecule crosslinking/polymerization is formed, to generate supermolecule hydrogen bond action during dynamic aggregation object subsequent forming, but The present invention is not limited only to this.
In embodiments of the present invention, make except through forming hydrogen bond between hydrogen bond group present in the polymer With outer, the hydrogen bond group can also be passed through form hydrogen bond with the hydrogen bond group in the other components that introduce as additive and make With.Such other components that can participate in being formed hydrogen bond action include but is not limited to small molecule, inorganic material, metal material, Contained in hydrogen bond group can be arbitrarily can with the hydrogen bond group formed hydrogen bond group.Between such other components Hydrogen bond can be formed.
In embodiments of the present invention, it is described based on the commutative covalent bond of alkyl triazole preferably by containing triazolyl Derivative and halogenated alkyl compounds react, can carry out before the generation of dynamic covalent cross-linking or in the process.
Wherein, group or segment containing the commutative covalent bond based on alkyl triazole contain the derivative of triazolyl And introducing for halogenated alkyl can use any appropriate reaction, include but are not limited to Types Below: isocyanates and ammonia The reaction of base, hydroxyl, sulfydryl, carboxyl, epoxy group, carboxylic acid, carboxylic acid halides, acid anhydrides, active ester and amino, hydroxyl, sulfydryl react, and third Olefin(e) acid ester radical reaction, acrylamide radical reaction, double bond radical reaction, epoxy group and amino, hydroxyl, sulfydryl it is anti- It answers, phenol-formaldehyde reaction, nitrine-alkynes click-reaction, tetrazine-norbornene reaction, silicone hydroxyl condensation reaction；Preferred isocyanate and ammonia The reaction of base, hydroxyl, sulfydryl, carboxylic acid halides, acid anhydrides and amino, hydroxyl, sulfydryl react, free radical acrylate reaction, acryloyl Amine radical reaction, double bond radical reaction, epoxy and amino, hydroxyl, sulfydryl react.
Wherein, the triazolyl derivative can directly select the raw material being commercialized, as an example, including but not only It is limited to such as 1- phenyl -4- methanol-based -1H-1,2,3- triazole, [1- (phenyl methyl) -1,2,3- triazole-4-yl] methanol, 1H-1, 2,3- triazole -1- acetic acid, 1- benzyl -1,2,3- triazole -4,5- dicarboxylic acids, iodo- 1- methyl-[1,2,3] triazole of 5-, 5- ethyl - 1- phenyl -1H- [1,2,3] triazole -4- formic acid, 4- [1,2,3] triazol-1-yl-piperidines, 1- phenyl -1H- [1,2,3] triazole -4- Methyl formate, 4,5,6,7- tetrahydro -1,2,3- triazole simultaneously [1,5-A] pyrazine hydrochloride, 4- ([1,2,3] triazol-1-yl) benzene Formaldehyde, 1- methyl -4- amino -1,2,3- triazole, 5- amino -1- benzyl -1H-1H-1,2,3- triazole -4- formamide etc..
Wherein, the triazolyl derivative can also be obtained by any appropriate reaction, wherein it is preferred that by alkynes and nitrine Reaction obtains, more preferably it is solvent-free, without catalyst under conditions of directly heat small molecule containing alkynyl/oligomer, containing azido Small molecule/oligomer and/or small molecule/oligomer simultaneously containing alkynyl and azido react to obtain.
Wherein, the halogenated alkyl compounds can directly select the raw material of commercialization, can also be by any appropriate Reaction obtains, and preferably directly selects the raw material being commercialized.As an example, the available halogenated alkyl compounds being commercialized It is including but not limited to following to be lifted: dibromoalkane hydro carbons, such as 1,2- Bromofume, 1,3- dibromopropane, the bromo- 2- methyl of 1,3- bis- Propane, the bromo- 2,2- dimethylpropane of 1,3- bis-, the bromo- 2,2- diethyl propane of 1,3- bis-, 1,4- dibromobutane, 1,5- dibromo penta Alkane, the bromo- 3- methylpentane of 1,5- bis-, 1,6- dibromo-hexane, 1,7- dibromo-heptane, bis- bromooctane of 1,8-, 1,9- dibromo nonane, 1, 10- dibromo-decane, 1,12- dibromo-dodecane, bis- bromopen tadecane of 1,15-, bis- bromo-octadecane of 1,18- etc.；Three bromo alkanes, such as 1,2,3- tribromopropane, tri- bromobutane of 1,2,4-, 1,3,5- tri- (bromomethyl) benzene, 1,3,5- trisbromomethyl -2,4,6- trimethyl Benzene etc.；Bromo alkylol, as ethylene bromohyrin, the bromo- 1- propyl alcohol of 2,3- bis-, the bromo- 2- propyl alcohol of 1,3- bis-, the bromo- 1- propyl alcohol of 3-, 4- are bromo- The bromo- 1- amylalcohol of n-butyl alcohol, 5-, the bromo- 1- hexanol of 6-, the bromo- 1-heptanol of 7-, the bromo- 1- octanol of 8-, the bromo- 1 nonyl alcohol of 9-, the 10- bromo- 1- last of the ten Heavenly stems The bromo- 1- undecyl alcohol of alcohol, 11-, the bromo- DODECANOL, 1- of 12-, the bromo- 1- tetradecanol of 14-, the bromo- 1- hexadecanol of 16-, dibromo new penta Glycol, the bromo- 2,3- butanediol of 1,4- bis-, the bromo- 2- butanol of 1,4- bis-, 2- (bromomethyl) -2- (methylol) -1,3- propylene glycol, two Bromine mannitol, tribromoneoamyl alcohol, 2,6- bis- (bromomethyl) -4- methylphenol etc.；Bromo alkyl acid, as bromoacetic acid, 3- bromo-propionic acid, 2,3- dibromo-propionic acid, 4- bromo-butyric acid, 5- bromine valeric acid, 11- bromine undecanoic acid, 16- bromine hexadecanoic acid etc.；Other bromine-containing compounds, such as The bromo- 1- hexene of bromopropene, 6-, 3- propargyl bromide, the positive butine of 4- bromine, the positive pentyne of 5- bromine, bromo-oligoethylene glycol-bromo, (2- bromine Methyl) chlorobenzoyl chloride, 4- bromobutanoylchloride, 6- bromine caproyl chloride, the bromo- 1- propanethiol of 3-, 6- bromine hexylamine etc.；Two iodo-alkyl chemical combination Object, such as 1,2- ethylidene periodide, 1,3- diiodo propane, the iodo- 2- methylpropane of 1,3- bis-, iodo- 2, the 2- dimethylpropane of 1,3- bis-, 1, Bis- iodobutane of 4-, bis- iodopentane of 1,5-, bis- iodohexane of 1,6-, the iodo- 3,3,4,4- tetrafluoro hexane of 1,6- bis-, 1,7- diiodo- heptane, 1,8- diiodo-octane, bis- iodononane of 1,9-, 1,10- diiodo- decane, 1,12- diiodo- dodecane etc.；Iodo-alkyl alcohol, such as 2- iodine second Alcohol, 3- iodine propyl alcohol, the iodo- 2- propyl alcohol of 1,3- bis-, the iodo- n-butyl alcohol of 4-, the iodo- 1- amylalcohol of 5-, the iodo- 1- hexanol of 6-, the iodo- 1-heptanol of 7-, The iodo- 1- octanol of 8-, the iodo- 1 nonyl alcohol of 9-, the iodo- 1- decyl alcohol of 10-, the iodo- 1- undecyl alcohol of 11-, the iodo- DODECANOL, 1- of 12- etc.；Idoalkane Base acid, such as iodoacetic acid, 4- iodine butyric acid；Other contain iodine compound, as 3- iodopropylene, the iodo- 1- amylene of 5-, 5- iodine ethyl valerate, (the iodomethyl) -1,4- of 2,5- bis- dioxanes, iodo-oligoethylene glycol-iodo etc..
In embodiments of the present invention, the generation and/or introducing of hydrogen bond group can before the generation of dynamic covalent cross-linking, It carries out later or in the process, any appropriate reaction can be used, included but are not limited to Types Below: isocyanates and ammonia The reaction of base, hydroxyl, sulfydryl, carboxyl, free radical acrylate reaction, double bond radical reaction, double bond cyclization, epoxy with The reaction of amino, hydroxyl, sulfydryl, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, amide Change reaction, the reaction of tetrazine-norbornene, active ester and amino, hydroxyl, sulfydryl react, silicone hydroxyl condensation reaction；It is preferred that isocyanide Acid esters and amino, hydroxyl, sulfydryl react, the reaction of urea-amine, amidation process, active ester and amino, hydroxyl, sulfydryl Reaction.The generation and/or introducing of hydrogen bond group can have one or the reaction type more than it, reaction means and structure.
In embodiments of the present invention, for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalent bond and hydrogen bond The ingredient of group, hydrogen bond group and hydrogen bond group can be small molecule and/or polymer segment.Polymer segment therein, packet Including but being not limited only to main chain is carbon-chain structure, carbon heterochain structure, carbon chain structure, element chain structure, element heterochain structure, carbon The polymer segment of miscellaneous element chain structure.The carbon-chain structure is the structure that main chain backbone contains only carbon atom；The carbon Heterochain structure is that main chain backbone contains carbon atom and any or several heteroatomic structures simultaneously, wherein the hetero atom packet Include but be not limited only to sulphur, oxygen, nitrogen；The carbon chain structure be main chain backbone contain simultaneously carbon atom and it is any or appoint it is several The structure of kind Elements Atom, wherein Elements Atom includes but are not limited to silicon, boron, aluminium；The element chain structure is main chain bone Frame is only containing the structure of Elements Atom；The element heterochain structure is main chain backbone simultaneously and only containing at least one hetero atom With the structure of at least one Elements Atom；The miscellaneous element chain structure of the carbon is that main chain backbone includes simultaneously carbon atom, hetero atom With the structure of Elements Atom.In an embodiment of the invention, it is carbochain knot that the preferably described polymer segment, which is main chain, The polymer segment of structure and carbon heterochain structure, because of its structure-rich, has excellent performance.As an example, preferred carbochain and carbon heterochain Polymer segment is included but are not limited to such as acrylic polymer, saturation of olefins quasi polymer, ethylenic unsaturation hydrocarbon-based polymeric Object, halogen-containing olefin polymer, polyacrylonitrile quasi polymer, polyvinyl alcohol based polymer, gathers polystyrenic polymer (2- oxazoline) quasi polymer, polyether-based polymers, polyester polymer, Biopolvester quasi polymer, polycarbonate polymer, Polyurethane polymer, polyureas quasi polymer, polyamide polymers, polyamine quasi polymer, liquid crystal quasi polymer, epoxy are birdsed of the same feather flock together Close the homopolymer, copolymer, modifier, derivative etc. of object, polysulfide ether polymer etc..In another embodiment of the invention In, preferably the polymer segment is element heterochain structure, by way of example, such as all kinds of poly-organosilicon polymer.In the present invention Another embodiment in, the glass transition temperature of the preferably described polymer segment is not higher than 25 DEG C, more preferably described The glass transition temperature of polymer segment be not higher than 0 DEG C, be presented as flexibility at room temperature before the reaction, it is convenient at normal temperature The processing preparation for carrying out subsequent products facilitates and obtains flexible and viscosity product, is also convenient for by increasing crosslink density or use Other additives adjust the hardness of material matrix, are conducive to embody the dynamic of supermolecule hydrogen bond as matrix.In this hair In bright another embodiment, preferably the glass transition temperature of the polymer segment is higher than 25 DEG C but lower than 40 DEG C, Be conducive to introduce the characteristics such as temperature sensitivity, moderate elasticity and dynamic.In yet another embodiment of the present invention, preferably Dissociation temperature (about 98 of the glass transition temperature of the polymer segment not less than 40 DEG C and not higher than dynamic covalent bond DEG C), be conducive to introduce the characteristics such as shape memory, high temperature dimensional stability, low temperature and room temperature hardness.As an example, preferably Polymer segment includes but are not limited to acrylic polymer, saturation of olefins quasi polymer, ethylenic unsaturation hydrocarbon-based polymeric Object, halogen-containing olefin polymer, poly- (2- oxazoline) quasi polymer, polyether-based polymers, polyester polymer, Biopolvester The homopolymer of quasi polymer, polyurethane polymer, polyureas quasi polymer, polysulfide ether polymer, silicone-based polymers etc., Copolymer, modifier, derivative etc..Specifically, as an example, currently preferred polymer segment includes but are not limited to gather Methyl acrylate, polyethyl acrylate, butyl polyacrylate, polyethylene, polypropylene, polystyrene, polyisobutene, polybutadiene Alkene, polynorbornene, polyisoprene, polyvinyl chloride, poly- (2- oxazoline), polyethylene glycol, polypropylene glycol, gathers oneself at polycyclic octene Lactone, poly- limonene carbonic ester, poly-β-hybroxybutyric acid, polycarbonate, polyurethane, polyureas, polyamide, polythiaether, poly- silicon oxygen Homopolymer, copolymer, modifier, derivative of alkane etc. etc..
In embodiments of the present invention, for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalent bond and hydrogen bond Group, the small molecule of hydrogen bond group and hydrogen bond group and/or polymer segment and/or dynamic aggregation object can have any conjunction Suitable topological structure includes but are not limited to linear chain structure, branched structure (including but not limited to starlike, H-type, dendroid, comb It is shape, hyperbranched), cyclic structure (including but not limited to monocycle, polycyclic, bridged ring, grommet, torus), two-dimensional/three-dimensional cluster structure and Its two kinds or several combination；Wherein, the linear chain structure of synthesis and control structure, the branched structure of structure-rich are preferably facilitated With can be with the two-dimensional/three-dimensional cluster structure of local enhancement, more preferable linear chain structure and branched structure.In the present invention, or even not It excludes to carry out the reaction such as further polymerized/cross-linked and connection using the polymer beads of crosslinking.
Selected above-mentioned each quasi polymer and its segment in the present invention, i.e., have hydrogen bond base containing dynamic covalent bond simultaneously again The polymer and its segment of group, the polymer for not only not contained dynamic covalent bond but also not contained hydrogen bond group and its segment only contain Polymer and its segment and only polymerization containing hydrogen bond group without dynamic covalent bond of the dynamic covalent bond without hydrogen bond group Object and its segment can directly select the raw material of commercialization, can also voluntarily polymerize.Polymerization is according to selected polymer Type includes but is not limited to polycondensation, addition polymerization and ring-opening polymerisation；Wherein, addition polymerization includes but is not limited to free radical polymerization, activity freedom Base polymerization, anionic polymerisation, cationic polymerization, coordination polymerization etc..Wherein, polymerization process can carry out in a solvent, can also be with It is solvent-free bulk polymerization.Specifically, as an example, the available polymerization of the present invention includes but is not limited to: styrene Class, the heat of (methyl) acrylic ester monomer cause general radical polymerization, phenylethylene, (methyl) acrylic ester monomer Light lnduced Free Radicals polymerization, the Iniferter free radical polymerization of vinyl chloride monomer, phenylethylene, (methyl) acrylic acid The atom transfer radical polymerization (ATRP) of esters monomer, phenylethylene, (methyl) esters of acrylic acid, acrylonitrile monomer are reversible Addition-fracture transferring free-radical polymerization (RAFT), nitroxide-mediated stable free-radical polymerization (NMP), ethylene, propylene coordination polymerization, benzene second The anionic polymerisation of vinyl monomer, lactone ring opening polymerization, lactams ring-opening polymerisation, epoxy addition polymerization, binary acid and dihydric alcohol Between polycondensation, the polycondensation between binary acid and diamine, between binary mercaptan and binary alkene/alkynes click-reaction polymerization, two Click-reaction polymerization between first nitrine and binary alkynes, the ring-opening polymerisation of 2- oxazoline derivative, polyurethane/polyurea reaction etc..? In specific implementation process, raw materials of compound can utilize above-mentioned any polymerisation process, appoint by the way that this field is general A kind of suitable polymerization technique is implemented, to obtain dynamic aggregation object of the invention.
It can be addition-crosslinked or condensation cross-linking for the mechanism of crosslinking of polymer.Wherein, it is addition-crosslinked refer to pass through addition Form and the cross-linking polymerization carried out, usually by the addition reaction containing multi-functional strand by intermolecular functional group And cross-linking products are formed, it is generated without by-product.Condensation cross-linking refers to the cross-linking reaction carried out by condensed forms, usually By forming cross-linking products by intermolecular functional group's condensation reaction containing multi-functional strand, there is by-product generation.
In embodiments of the present invention, crosslinking can be using any appropriate physics and chemical crosslinking technique.Physics is handed over Connection technique includes but is not limited to heat initiation crosslinking, photo-initiated crosslinking, radiation-induced crosslinking, plasma causes crosslinking, microwave draws Hair crosslinking etc.；Chemical crosslinking technique includes but is not limited to peroxide crosslinking, nucleopilic reagent substitution crosslinking, isocyanates reaction friendship Connection, epoxy reaction crosslinking, acrylate reactions crosslinking etc..Cross-linking process can be carried out in the form of ontology, solution, lotion etc..When Using bulk form, solid end product is conveniently directly obtained；When using solution form, gel is conveniently directly obtained；When using cream Liquid mode facilitates and obtains particle dispersing but with tack.It should be pointed out that any crosslinking must assure that the dynamic Covalent bond complete is incompletely dissociated the disintegration that can lead to covalent cross-linking network.
Initiator needed for above-mentioned polymerization, cross-linking method and polymerization, cross-linking process, catalyst, crosslinking agent, other Auxiliary agent and reaction condition etc. are all open known routine techniques (such as Pan Zuren chief editor, " polymer chemistry (enhanced editions) "), Those skilled in that art, which can according to need, to be reasonably selected and combines.
It is illustrated below for the embodiment of the part preparation method of network structure of the invention.
For example, second of network structure of the invention can be prepared by following methods: hydrogen bond group (following structures will be had R is denoted as in formulaH) monomer with at least two halogen atom X halogenated alkyl compounds is blended heating reaction, it can gather Close/be cross-linked to form second of network structure in the present invention.It, can by controlling the formula rate of raw material and the molecular weight of monomer With the content and ratio of each hydrogen bond group on dynamic covalent bond in regulating networks and different location, make the covalent cross-linking in network Reach covalent gel point or more.
For another example, second of network structure of the invention can be prepared by following methods: will have side hydrogen bond group RHIt is double Acyl chlorides monomer and (V is denoted as in following structural formula containing the commutative covalent bond based on alkyl triazolem) trihydroxy monomer it is total With reaction, second of network structure in the present invention can be formed with polymerized/cross-linked.By the formula rate and list that control raw material The molecular weight of body, in adjustable network on dynamic covalent bond and different location each hydrogen bond group content and ratio, make net Covalent cross-linking in network reaches covalent gel point or more.
For another example, second of network structure of the invention can also have the polymer of triazolyl and side hydrogen bond group by side group Realization is reacted with the halogenated alkyl compounds of difunctionality: will have side group hydrogen bond group RHWith at least two triazolyl TrPolymerization Object is reacted with the halogenated alkyl compounds at least two halogen atom X, second of network knot in the available present invention Structure.By control hydrogen bonds group and the formula rate for being free of hydrogen bond group monomer, in adjustable network dynamic covalent bond with The ratio of hydrogen bond group is crosslinked the supermolecule in network and reaches gel point or more.
The embodiment of other network structures in the present invention is similar, and those skilled in the art can be according to this hair Bright understanding selects suitable preparation means, reaches ideal purpose.
In the present invention, two classes can be classified as according to polymers compositions crosslinking situation in composition interpenetrating networks, it is Semi-IPN With full interpenetrating.Only a kind of component is covalent cross-linking in Semi-IPN, and another component is worn in the form of non-covalent strand It inserts and becomes entangled in covalent cross-linking component.
Traditional interpenetrating net polymer preparation method generally includes one-step method interpenetrating and two-step method interpenetrating.One-step method i.e. one All the components are added secondary property, then carry out polymerized/cross-linked, prepare target network.Two-step method first prepares the 1st network polymerization And then object is immersed in the monomer/pre-polymer solution to form the 2nd network, then it is miscellaneous to obtain target for initiation polymerized/cross-linked Change network.The preparation of dynamic aggregation object in the present invention can also use one-step method interpenetrating and two-step method interpenetrating, in specific condition Down must also using three steps and its more than method.
It is illustrated below for the embodiment of the part preparation method of interpenetrating net polymer of the invention.With It is lower to lift only as an example, it not limits the scope of the invention, is lifted the present invention is not limited to following.
For example, the dynamic aggregation object is made of two networks in the 5th kind of network structure of the invention.Firstly, system Hydrogen bond group is not present in standby one kind, but there is the polymer of the commutative covalent bond based on alkyl triazole on polymer chain skeleton Dynamic covalent cross-linking network.Then, gained dynamic covalent networks are swollen, with the monomer or prepolymer of supermolecule cross-linked network, Crosslinking agent etc. be uniformly mixed, carry out supermolecule crosslinking, thus obtain full interpenetrating net polymer namely Supramolecular Network dispersion pass through It is through in dynamic covalent cross-linking.Alternatively, by monomer or prepolymer, the crosslinking agent and supermolecule cross-linked network of dynamic covalent cross-linking network The monomer or prepolymer of network, crosslinking agent etc. are uniformly mixed, while carrying out dynamic covalent cross-linking and supermolecule crosslinking to get to this hair The 5th kind of bright network structure.
For another example, in the 8th kind of network structure of the invention, firstly, reasonably selecting preceding method preparation simultaneously containing dynamic The cross-linked network with second of network structure of covalent cross-linking and supermolecule crosslinking.Then, by resulting cross-linked network and super Molecularly Imprinted Polymer is sufficiently blended to arrive semi-interpenetrating network polymer.Alternatively, will have the hybrid cross-linked of second of network structure Monomer or prepolymer, the crosslinking agent of network are uniformly mixed with supermolecule polymer, go forward side by side Mobile state covalent cross-linking to get this hair is arrived The 8th kind of bright network structure.
In the present invention, the dynamic aggregation object and the form containing its composition can be ordinary solid, elastomer, Gel, foam etc..Wherein, the dissolvable small-molecular-weight component content contained in ordinary solid and foamed material is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Ordinary solid mechanical property is good, elasticity Mechanics moderate performance but has the unexistent flexibility of ordinary solid, preparation method is also most easy, therefore more preferably.Foam Since light and hardness and bendable folding endurance are adjustable, and purposes is wide；In addition, foam itself also has certain buffer capacity, The energy absorption performance that in energy-absorbing method of the invention there is collaboration to be promoted, therefore also more preferably.In embodiments of the present invention, Sweller can be introduced in hydridization dynamic aggregation compositions, prepare hydridization dynamic aggregation compositions gel.Gel products Flexibility and bendable folding endurance are all good, and can have certain toughness by structure and formula adjustment, because there are sweller, The unexistent beneficial constituent of material of many other forms can be incorporated, there is special purposes.Wherein, the swelling Agent can include but is not limited to organic solvent, ionic liquid, oligomer, plasticizer, water, and it is organic molten accordingly to obtain dynamic aggregation object Agent gel, ionic liquid gel, oligomer swell gel, plasticizer swell gel, hydrogel.Wherein, preferred ion liquid is solidifying Glue and plasticizer swell gel.
A kind of preferred preparation method of dynamic aggregation object sweller swell gel of the invention includes but is not limited to following step It is rapid: each raw material for preparing dynamic aggregation object and other raw materials being added in sweller and optional solvent, preparation dynamic is made The sum of each material quality score of polymer be 0.5~70%, polymerize by the appropriate means, be coupled, is crosslinked or its The chemical reaction of his type removes solvent as needed after reaction, that is, dynamic aggregation object swelling solvent swell of the invention is made Gel.The preferred preparation method of another dynamic aggregation object sweller swell gel of the invention includes but is not limited to following step It is rapid: the dynamic aggregation object and other raw materials being swollen in sweller and optional solvent, the dynamic aggregation object is made Mass fraction be 0.5~70%, sufficiently remove solvent as needed after swelling, that is, a kind of dynamic aggregation object swelling solvent swell be made Gel.
In embodiments of the present invention, the dynamic aggregation object can be prepared into foamed material.Wherein, foam includes soft Sex vesicle foam or semi-flexible, semi-rigid, micropore or rigid foam.
In embodiments of the present invention, the structure of the dynamic aggregation object foamed material is related to open-celled structure, closed pore Three kinds of structure, half-open semi-closure structure etc..It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three Dimension can be transferred through gas or liquid, and abscess diameter is 0.01 to 3mm etc..Hole-closing structure has individual blisters structure, inner cell There is wall film to separate between abscess, the overwhelming majority is not interconnected, and abscess diameter is 0.01 to 3mm etc..Contained abscess It is existing to be interconnected again that have mutual disconnected structure be then half open-celled structure.
In embodiments of the present invention, foaming method is usual way, can be divided according to the difference of foaming agent used For physical blowing method and chemical blowing process two major classes.Foam can have water or it is anhydrous under the conditions of prepare, mechanical can send out Bubble or on-mechanical foaming.Further, the non-reacted foaming agent of auxiliary known in the art can be used in the preparation of foam.
A kind of preparation method of preferred dynamic aggregation object foam of the present invention includes the following steps: in preparation single network When dynamic aggregation object foam, two component reaction materials are first prepared.Reaction mass one includes all small points for generating dynamic aggregation object Sub- monomer, chain extender, crosslinking agent and the auxiliary agent needed for other；Reaction mass two includes foaming agent, foam stabiliser, for urging The catalyst and the auxiliary agent needed for other for changing foaming and/or polymerization crosslinking reaction.Then by two component reaction materials according to one Certainty ratio mixing, stirring, and temperature control, the single network dynamic aggregation object to be foamed are carried out as needed.By this preparation The dynamic aggregation object that method prepares dynamic aggregation object foam is preferably based on the polymer of polyurethane, polyureas.
The preparation method of another preferred dynamic aggregation object foam of the invention is freeze-drying, is included the following steps: The dynamic aggregation object for swelling in volatile solvent is freezed, then escaped in a manner of distillation close under vacuum condition it is molten Agent.During solvent evolution and after evolution, polymer can maintain the shape before freezing, thus obtain porous spongy Foamed material.
In dynamic aggregation object foam preparation processes of the invention, when containing multiple polymer networks in foam, multiple nets Network can generate simultaneously, can also be separately generated.
Dynamic aggregation object foamed material provided by the present invention further relates to: by welding, gluing, cutting, matching plane, perforation, The dynamic aggregation object foamed material, is transformed into any shape that needs by coining, lamination and hot forming, for example, pipe, stick, Sheath, container, ball, piece, volume and band；By lamination, bonding, fusion and other interconnection techniques, the dynamic aggregation object is steeped It is combined together with other materials known to foam material and sheet material, film, foam, fabric, stiffener and those skilled in the art As complicated interlayer structure；Purposes of the dynamic aggregation object foamed material in washer or sealing；The dynamic aggregation object Purposes of the foamed material in packaging material or in a reservoir.About dynamic aggregation object of the invention, foamable dynamic aggregation object It is such a type, allows to through other formings skill known to extrusion, injection molding, compression moulding or those of skill in the art Art deforms them.
Foamed material provided by the present invention is different from common foamed material, three-dimensional prepared by common foamed material Once being formed, structure cannot change structure again, repair difficulty, not can be recycled after damaged.Due to foaming material provided by the present invention Material can also be repaired after rupturing under certain condition although the macromolecule network of covalent cross-linking, or pass through plastotype again Or reclaiming is done him and is used, there are hydrogen bond actions and dynamic covalent bond while reason is in network structure.Institute of the present invention The foamed material of offer solves the problems, such as plastotype again, controllable reparation and the reclaiming of regular-type foam material.
Dynamic aggregation object material of the invention during the preparation process, can be in the range of not interfering the object of the invention According to circumstances selection is added or used to other polymers, auxiliary agent, filler, sweller and carrys out formula group collectively as dynamic aggregation object Point, material processing performance can be improved, improved product quality and yield, product cost is reduced or assign product certain is peculiar Application performance, but these additives or using object it is not necessary to.
Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, It can be selected from natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and is had Some molecular weight can be oligomer or high polymer according to the difference of molecular weight without limitation, according to the difference of polymeric species, Can be homopolymer or copolymer, in the specific use process should be according to the performance of target material and the need of actual fabrication process It wants and is selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..
When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, polyamides Imines, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polyphenyl second Alkene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl ester are total Polymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-acetate Ester copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), polyisoprene, gather it is suitable Butadiene, styrene-butadiene copolymer, hycar, poly- (the chloro- 1,3- butadiene of 2-), isobutene-are different Pentadiene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene- Ethylidene norbornene copolymer, dimethyl silicone polymer, Polymethyl methacrylate, polymethylphenylsiloxane, poly- methyl Vinyl benzene radical siloxane, poly- methyl ethylene trifluoropropyl siloxane, vinylidene-chlorotrifluoroethylene, inclined fluorine second Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, polycyclic oxygen Chloropropane, epichlorohydrin ethylene oxide copoymer, epoxychloropropane-ethylene oxide-propylene oxide copolymer etc..
Wherein, the type of other polymers used does not limit, mainly depending on required material property；Used The dosage of other polymers is not particularly limited, generally 1-50wt%.
Wherein, the auxiliary agent may include but be not limited to the combination of following one or more, such as additive synthesis, including catalysis Agent, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, fire retardant；Improve The auxiliary agent of mechanical property, including toughener, coupling agent；Improve the auxiliary agent of processing performance, including solvent, lubricant, release agent, increasing Mould agent, thickener, thixotropic agent, levelling agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；Other are helped Agent, including antistatic agent, biocide mildewcide, foaming agent, foam stabiliser, nucleating agent, rheological agent etc..
Catalyst in the auxiliary agent can reduce reaction activity by changing reaction path to accelerate to react The reaction rate of object during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. polyurethane closes At with catalyst: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- dimethylamino- Ethyoxyl) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) two Isopropanolamine, N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyleyelohexane Amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethyl ethanol Amine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, dioctyl tin two Laurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, phenylmercuric acetate, propionic acid Benzene mercury, 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, tri-chlorination Titanium, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter Ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc.；3. CuAAC catalysts: by monovalence Copper compound and amine ligand share concerted catalysis；Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine Ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] amine (TBTA), three [(1- tert-butyl -1H-1,2,3- Triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；④ Thiol-ene catalysts: photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy Base -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethylamino pyrrole Pyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01-0.5wt%.
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: 1. free radical Polymerization initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), dicetyl peroxydicarbonate diisopropyl Bis- (4- tert-butylcyclohexyl) esters of ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tert-butyl hydroperoxide benzoic acid Ester, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azo two Isobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization causes Agent: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system；3. from Son polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system；4. matching Position polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；5. ring-opening polymerisation With initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, the preferred mistake of initiator Aoxidize lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, and one As be 0.1-1wt%.
Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, guarantee that material can be suitable It is processed and is prolonged its service life sharply, include but are not limited to following any or appoint several antioxidant: Hinered phenols, Such as 2,6 di tert butyl 4 methyl phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol)；Sulfur-bearing by Hinder phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert-butylphenol]； Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization isocyanide Acid esters Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) P-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thiodipropionic acid dilauryl Osmanthus ester, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, three nonyl benzene of phosphorous acid Ester, three [2.4- di-tert-butyl-phenyl] 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-phenyl] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) 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, prolong 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；Ultraviolet absorbing agent, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyl Base -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, (the 2- hydroxyl of 2,4,6- tri- Base -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl；Pioneer's type is ultraviolet Light absorbers, such as the p- tert-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 acid 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 piperidine) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamate, N, positive fourth positive group aminodithioformic acid nickel of N '-two etc.；Its In, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used is stablized Agent dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent enables to polymer samples in processing or use process 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；Composite thermal stabilizer, such as altogether Precipitate metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer etc.；Wherein, the preferred barium stearate of heat stabilizer, Calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not limit especially It is fixed, generally 0.1-0.5wt%.
Dispersing agent 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 the solid and liquid particles in liquid for uniform dispersion, while can also prevent particle Sedimentation and cohesion form stable suspension comprising but be not limited only to following any or appoint several dispersing agents: anionic, Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as aliphatic alcohol polyethenoxy Ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, such as starch, bright Glue, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonates, polyvinyl alcohol Deng.Wherein, the preferred neopelex of dispersing agent, naphthalene system methylene sulfonate (dispersing agent N), aliphatic alcohol polyethenoxy Ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.
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 comprising but be not limited only to following any or appoint several Kind emulsifier: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, Negel, succinic acid Sulfonated ester, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, phosphate ester salt, Fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylate Type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, rouge Fat acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite And sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferably neopelex, lose Water Span, triethanolamine stearate (Emulphor FM), emulsifier used are not particularly limited, generally For 1-5wt%.
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- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromopropyl) anti-butylene 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%.
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 copolymerization 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 to make 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- epoxy) propyl trimethoxy Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
Solvent in the auxiliary agent, adjustable viscosity are convenient for technological operation, make in product preparation process or in preparing With.Its include but are not limited to it is following any or appoint it is several: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride, Chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydro furan Mutter, dioxane), esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol list first Ether acetate), dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) etc..Solvent usage used is not particularly limited, Generally 1-200wt%.
Lubricant in the auxiliary agent can be improved 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 fatty 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 stearamide；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%.
Release 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 release 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, polyvinyl alcohol Deng；Wherein, the preferred dimethicone of release agent, polyethylene glycol.Release 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, 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- ethyl) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as The own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy rouge Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyl), epoxy soybean Oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box methyl acetylricinolate, binary Alcohol lipid, such as the sour glycol ester of C5~9, the sour Triethylene Glycol of C5~9；Class containing chlorine such as afforests paraffin class, chlorinated fatty acid Ester；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, trimellitic acid Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), neighbour Dibatyl phithalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene two Formic acid diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Thickener in the auxiliary agent, can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, and one As used during production of the invention and semi-finished product store comprising but be not limited only to following any or appoint several thickenings Agent: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulfate, alkyldimethylamine oxide, fatty acid monoethanol Amide, fatty diglycollic amide, fatty acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut monoethanolamide Propyl betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazole quinoline, titanate coupling agent；Polymer substance, such as bentonite, manually Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch, Seaweed acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide, Polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc.；Wherein, the preferred hydroxy ethyl fiber of thickener Element, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally For 0.1-1.5wt%.
Thixotropic agent in the auxiliary agent is added in polymeric system, increases the thixotropy of polymeric system.Including but not It is only limitted to following any or appoints several: gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silica derivative, urea Derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt%.
Levelling agent in the auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, 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, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, the preferred poly dimethyl of levelling agent Siloxanes, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
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 does not need to 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- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene) Double benzoxazoles (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: sedimentation 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%.
The deleterious charge assembled in polymer samples can be guided or be eliminated, make it by the antistatic agent in the auxiliary agent Production and life are not brought inconvenience or are endangered comprising but be not limited only to following any or appoint several antistatic agents: yin from Subtype antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, alkyl phenol Polyoxyethylene groups ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, alkyl polyoxyethylene base ether sulfonic acid triethanolamine, phosphoric acid Ester derivant, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl bis- [two (2- ethylol amine)] phosphates, phosphate Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, N, N- cetyl-ethyl morpholine ethyl-sulfate salt, stearamide propyl (2- hydroxyl second Base) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2- alkyl -3,3- dihydroxy ethyl imidazoline perchlorate, 2- Heptadecyl -3- ethoxy -4- carboxymethyl imidazoline, N, bis- (α-ethoxy)-N-3 (dodecyloxy -2- hydroxypropyl) first of N- Ammonium Methylsulfate salt；Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- tri- Alkylammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid sodium of N- lauryl-N, N-, alkyl two Salt hydroxide, -3 ethoxy -3- acetic acid alkali imidazoline quaternary amine alkali of 2- alkyl, N- alkyl amino acid in (polyoxyethylene) ammonium second Salt；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol epoxy second The polyethylene oxide of alkane addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, sorbitan mono-laurate Addition product；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol-terephthalic acid (TPA) such as ethylenediamine Ester -3,5- dibenzoate sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetonyl pyrrole Pyridine phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, octadecyldimethyl hydroxyl second Base quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used does not have It is particularly limited to, generally 0.3-3wt%.
Dehydrating agent in the auxiliary agent, can moisture in removing system comprising but be not limited only to it is following any or Appoint several: oxazolidine compound (such as 3- Ethyl-2-Methyl -2- (3- methyl butyl) -1,3- oxazolidine), different to Methyl benzenesulfonyl Cyanate, triethyl orthoformate, vinyl silanes, calcium oxide etc..Dehydrating agent dosage used is not particularly limited, generally 0.1-2wt%.
Biocide mildewcide in the auxiliary agent can inhibit the growth of bacterium, and the appearance for keeping product clean and tidy extends and uses Service life；Or protection user, the health for promoting user, such as reduce tinea pedis.It includes organic matter and inorganic matter, including but It is not limited only to following any or appoints several: isothiazolinone derivatives, such as 5-Chloro-2-methyl-4-isothiazolin-3-one, 2- Methyl -4- isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketone, octylisothiazolinone, 2,4,4- tri- Chlorine-2-hydroxyl-diphenyl ether, 2- (4- thiazolyl) benzimidazole, copper 8-quinolinolate or bis- (8-hydroxyquinoline base) copper；It is organic Tin compound, such as tributyl-tin fumarate, tributyltin acetate, bis- (tributyl tin) sulfide, bis- (tributyl tin) tin oxide； N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide；Inorganic compound or compound, such as nano silver, nano-silica Change titanium, nano silica, nano zine oxide, superfine cupper powder, inorganic antiseptic YY-Z50, XT inorganic antiseptic, composite antibacterial Agent KHFS-ZN.Biocide mildewcide dosage used is not particularly limited, generally 0.5-2wt%.
Foaming agent in the auxiliary agent can make polymer samples foaming pore-forming, to obtain light polymeric material Material comprising but be not limited only to it is following any or appoint several foaming agents: physical blowing agent, as carbon dioxide, nitrogen, argon gas, Methane, ethane, propane, butane, iso-butane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, toluene, Methyl ether, ether, petroleum ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane, hydrochlorofluorocarbons- 22, hydrochlorofluorocarbons -142b, hydrofluorocarbons -134a, hydrofluorocarbons -152a, chlorofluorocarbons -11, chlorofluorocarbons -12, chlorine fluorine Hydrocarbon -114；Inorganic foaming agent, such as sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate, carbonate ammonia natrium, azido compound, hydroboron Deng；Organic foaming agent, such as N, N '-dinitrosopentamethlyene tetramine, N, N '-dimethyl-N, N '-dinitroso paraphenylene terephthalamide Amine, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, two isobutyl of azo Nitrile, 4,4 '-oxobenzenesulfonyl hydrazide, 3,3 '-disulfonyl hydrazide diphenyl sulphone (DPS)s, 1,3- benzene Erhuang hydrazides, benzene sulfonyl hydrazide, three diazanyls three Piperazine, p-toluene sulfonylsemicarbazide, biphenyl -4,4 '-disulfonyl nitrine, diazo aminobenzene；Physical microballoon/granule foaming agent, such as The expandable microballoon of the companies such as Akzo Nobel production.Wherein, the preferably environmentally friendly carbon dioxide of foaming agent, nitrogen, argon Gas and sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (foaming agent of N '-dinitro H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent.Hair used Infusion dosage is not particularly limited, generally 0.1-30wt%.
Blowing promotor in the auxiliary agent comprising but be not limited only to foamed promoter, frothing inhibitor, foam and stablize Agent etc..The foamed promoter comprising but be not limited only to it is following any or appoint it is several: urea, stearic acid, lauric acid, Salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide, ZB- 530,KZ-110,MS-1；The frothing inhibitor comprising but be not limited only to following any or appoint several: maleic acid, richness Horse acid, stearyl chloride, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, Oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl Malaysia Sour tin etc.；The foam stabiliser comprising but be not limited only to it is following any or appoint it is several:: silicone oil, sulfonated aliphatic alcohol, Alpha-sulfonated fatty acid, NaLS, dodecyldimethylamine oxide, alkylolamides, polyethylene glycol oxide, alkylaryl are poly- Ethylene oxide alcohol, tridecyl ether, Polyoxyethylene sorbitan glycerol monolaurate, siloxanes-ethylene oxide are embedding Section copolymer etc..Blowing promotor dosage used is not particularly limited, generally 0.05-10wt%.
Nucleating agent in the auxiliary agent can accelerate 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 guarantee that polymer has good brushability and appropriate during film Coating thickness, the sedimentation of solid particle, can be improved 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, fumed silica, 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%.
The filler primarily serves following effect in polymer samples: 1. reducing the shrinking percentage of molded article, mentions Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjusting the viscosity of material；③ Meet different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, improve wearability, improve Heat distortion temperature improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability and chemically-resistant being rotten Corrosion；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The filler, selected from following any or appoint several fillers: inorganic non-metallic filler, organic is filled out at metal packing Material.
The inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, fullerene, carbon nanotube, molybdenum disulfide, Slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, Oil shale powder, swelling perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron cement, white clay, alkali mud, boron mud, glass microballoon, tree Rouge microballon, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanate are fine Dimension, silicon carbide fibre, ceramic fibre, whisker etc..In an embodiment of the invention, preferably conductive inorganic non- Metal packing includes but are not limited to graphite, carbon black, graphene, carbon nanotube, carbon fiber, facilitates and obtains electric conductivity and/or tool There is the composite material of electric heating function.In yet another embodiment of the present invention, preferably have and make in infrared and/or near infrared light With the lower non-metallic fillers with heating function, graphene, graphene oxide, carbon nanotube are included but are not limited to, is conveniently obtained Obtain the composite material heated using infrared and/or near infrared light.Good heating property, the especially fever of remote control property Performance help to obtain the performances such as controllable shape memory, selfreparing.In yet another embodiment of the present invention, preferably have There is the inorganic non-metallic filler of thermal conductivity, includes but are not limited to graphite, graphene, carbon nanotube, aluminium nitride, boron nitride, carbon SiClx facilitates the composite material for obtaining thermally conductive function.
The metal packing, including metallic compound include but are not limited to following any or appoint several: metal powder End, fiber comprising but it is not limited only to copper, silver, nickel, iron, gold etc. and its powder, the fiber of alloy；Nano-metal particle, packet Include but be not limited only to nanogold particle, nano-Ag particles, nanoparticle palladium, nano iron particles, nano cobalt granule, nano nickel Grain, nanometer Fe3O4Particle, nanometer γ-Fe2O3Particle, nanometer MgFe2O4Particle, nanometer MnFe2O4Particle, nano Co Fe2O4? Grain, nano Co Pt3Particle, nanometer Fe Pt particle, nanometer Fe Pd particle, ferronickel bimetallic magnetic nanoparticle and other red Outside, near-infrared, ultraviolet, the nano-metal particle that can be generated heat under at least one effect of electromagnetism etc.；Liquid metal comprising but not It is only limitted to mercury, gallium, gallium indium liquid alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Metallo-organic compound point Son, crystal and other in infrared, near-infrared, ultraviolet, the substance that can be generated heat under at least one effect of electromagnetism etc..In the present invention An embodiment in, can preferably carry out electromagnetism and/or near-infrared heating filler, include but are not limited to nanogold, Nano silver, Technique of Nano Pd, nanometer Fe3O4, to carry out remote sensing heating.In yet another embodiment of the present invention, preferably liquid is golden Belong to filler, the flexibility and ductility of substrate can be kept while enhancing the thermally conductive of flexible parent metal, electric conductivity.In the present invention Another embodiment in, preferably in infrared, near-infrared, ultraviolet, the organic gold that can generate heat under at least one effect of electromagnetism Belong to compound molecule, crystal, on the one hand facilitates compound, another side raising induction is generated heat efficiency and promote heating effect.
The organic filler includes but are not limited to following any or appoints several: 1. natural organic filler, such as natural Rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, lignin, starch, wood powder etc.；2. synthesizing Resin extender, such as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, acetate fiber Element, polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-acetate second Enoate copolymer, high density polyethylene (HDPE), high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine-first Urea formaldehyde, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, poly terephthalic acid fourth two Alcohol ester, polycarbonate, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate, Phenolic resin, tetrafluoroethylene-perfluoro propane copolymer, polyimides, polymethyl acrylate, polymethacrylonitrile, poly- methyl-prop E pioic acid methyl ester, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, gathers polyphenylene oxide Vinyl acetate, polyvinyl butyral, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyethylene Alcohol formal, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.；3. closing At gum filler, as 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.；4. synthetic fibers are filled out Material, such as viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polycarbonate, polyvinyl alcohol Fiber, polyester fiber, polyurethane fiber, polyacrylonitrile fibre, vinylon, polyvinyl chloride fibre, polyolefin are fine Dimension, fluorofibre, polytetrafluoroethylene fibre, aromatic polyamide fibre, aramid fiber or aramid fiber etc.；5. foamed polymer Composition granule and expandable polymer beads.
Wherein, wire feeding does not limit, mainly depending on required material property；Amount of filler used is without spy It does not limit, generally 1-30wt%.
Wherein, the sweller may include but be not limited to water, organic solvent, ionic liquid, oligomer, plasticizer.Its In, oligomer can also be considered as plasticizer.
Organic solvent in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several Kind: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride, chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), Ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrofuran, dioxane), esters (such as ethyl acetate, acetic acid fourth Ester), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol monomethyl ether acetate), dimethylformamide (DMF), N- methyl Pyrrolidones (NMP) etc..
Ionic liquid in the sweller is generally made of organic cation and inorganic anion, as an example, sun It includes but is not limited to that alkyl quaternary ammonium ion, alkyl quaternary are seen imidazol ion, the N- alkyl that ion, 1,3- dialkyl group replace that ion, which is selected from, Substituted pyridinium ion etc.；Anion be selected from include but is not limited to for halide ion, tetrafluoroborate ion, hexafluoro-phosphate radical from Son also has CF3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、 (C2F5SO2)2N-、SbF6 -、AsF6 -Deng.In ionic liquid used in the present invention, the preferred glyoxaline cation of cation, anion It is preferred that hexafluorophosphoricacid acid ions and tetrafluoroborate ion.
Oligomer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several: Polyethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid stone Wax etc..
Plasticizer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several: Phthalates: dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), dibutyl phthalate (DHP), diisooctyl phthalate (DIDP), diisononyl phthalate (DINP), neighbour Phthalic acid butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, as tricresyl phosphate (TCP), phosphoric acid (hexichol -2- ethyl) oneself Ester；Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy Glyceride type, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidised soybean oil, epoxystearic acid (2- second Base) own ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetyl Methyl ricinolcic acid, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests stone Wax class, chloro fat acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Petroleum sulphur Acid phenenyl ester, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, the preferred DBP, DOP of plasticizer, DIOP, DIDP, DINP, TCP, epoxidised soybean oil.Wherein, epoxidised soybean oil is that a kind of environment-friendly type plastic of function admirable increases Mould agent, epoxidation reaction preparation occurs for refined soybean oil and peroxide, in polymer product resistance to volatilization, it is not easy to migrate, Not easy to lose, this is to keeping product light, thermal stability and to prolong the service life be highly beneficial.Epoxidised soybean oil toxicity pole It is small, it is allowed for the packaging material of food and medicine by many countries, is that the unique of Food and Drug Adminstration of the US's approval can For the epoxy plasticiser of packaging material for food, therefore it is more highly preferred to.
In the preparation process of dynamic aggregation object, special limit is not done to the dosage 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.
A kind of energy-absorbing method based on dynamic aggregation object provided by the present invention is super when not containing in the dynamic aggregation object When molecule hydrogen bond is used for energy-absorbing, dynamic aggregation object is preferably prepared into elastomer-forming, gel or foamed material and carries out energy-absorbing；When described In dynamic aggregation object containing supermolecule hydrogen bond be used for energy-absorbing when, can be polymer fiber, film, profile, elastomer, foam, The variforms such as gel.When in dynamic aggregation object introduce supermolecule hydrogen bond action after, by network structure dynamic covalent bond and Supermolecule hydrogen bond combines, and dynamic and weaker bond energy using supermolecule hydrogen bond, especially strain-responsive generate crosslinking There is flexible and strong elasticity transformation, plays the role of effective disperses impact forces in the variation of degree；Furthermore supermolecule hydrogen bond have compared with Weak bond energy, when impacting sufficiently large, hydrogen bond can be dissociated and dissipation energy with that can sacrifice key-shaped formula；So can greatly improve dynamic The performances such as damping, damping, sound insulation, noise elimination, the defense of resistance to impact of state polymer composition, in life, production, movement, stop There is more extensive energy-absorbing purposes in the fields such as spare time, amusement, military affairs, police service, security, medical care.For example, can be by dynamic aggregation object group Close object material be applied to production damping shock absorber, for various motor vehicles, mechanical equipment, bridge, building vibration isolation, When being vibrated, the big energy that can dissipate plays damping, to effectively mitigate the vibration of vibration body；It is prepared into bullet Property body, foam and gel rubber material, so as to be applied to airborne and air-drop protection, collision prevention of vehicle, electronic apparatus article and precision machine The shock resistance of tool instrument and vibration damping protection etc., or athletic protective article, surge guard product, protector etc. is made for people Body, animal body, article etc. carry out defense of resistance to impact in daily life, production and movement, or for police protective materials of army etc. Aspect；It is prepared into explosion-proof tent, blanket, wall, bulletproof glass squeegee, sandwich plate etc., explosive-proof protector is carried out to article, reduces object Product or human body are including vibration and impact suffered under the external forces such as the shock wave that explosion generates；Further, it is also possible to design The energy-absorbing material of shape memory function is provided, is applied to specific occasion, prepares the energy-absorbing articles of personalized customization.It is dynamic with this State polymer is covalent and/or super using its after endergonic process causes material internal cracked or is broken as energy-absorbing material Molecule Motion state property, can carry out recycled after selfreparing in situ, be also convenient for recycling and reprocess.
The energy-absorbing method of the present invention based on dynamic aggregation object is done into one below with reference to some specific embodiments Step description.Specific embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
A kind of dynamic aggregation object ordinary solid based on polyester is prepared for energy-absorbing.
2- chlorine cyclohexanone is dissolved in methylene chloride, metachloroperbenzoic acid is added, keeps 2- chlorine cyclohexanone and m-chloro peroxide The molar ratio of benzoic acid is 10:12, and reaction obtains the chloro- 6-caprolactone 1a of α-.It is to draw with 1 molar equivalent ethyl alcohol under anhydrous condition Agent is sent out, using stannous octoate as catalyst, 40 molar equivalent 6-caprolactones, 10 molar equivalent compound 1a is dissolved in toluene and carry out ring Ester ring-opening polymerisation obtains the polyester that side group contains chlorine atom.The polymer that resulting side group contains chlorine atom is dissolved in dimethyl Formamide (DMF) is added the sodium azide with 2 molar equivalent of chlorine atom, converts azido for chlorine atom side group.Again by side group It is dissolved in tetrahydrofuran for the polymer and alkynes ethylbenzene of azido, the molar ratio both kept is 1:1, in cuprous iodide and pyridine Under catalysis, the polyester that side group contains triazolyl is obtained in 35 DEG C of reactions.Gained polyester and a certain amount of bis- bromooctane of 1,8- are total to It is mixed, it keeps the molar ratio of triazolyl and bromine atom for 4:5, and the mixed-forming at 120 DEG C, obtains dynamic aggregation object of the invention Product.This dynamic aggregation object can be used as the protective layer of Anti-impact shock-absorbing, selfreparing can be carried out after cracking, while having shape Shape memory function.
Embodiment 2
A kind of dynamic aggregation object plasticizer swell gel based on polynorbornene is prepared for energy-absorbing, supermolecule therein Effect is based on cyanuric acid derivative side group.
Cyanuric acid and the chloro- 1- hexene of 6- are kept into molar ratio 4:1, are dissolved in anhydrous dimethyl sulphoxide, is catalyzed in potassium carbonate Under be stirred to react at 80 DEG C 15 hours, obtain the olefinic monomer 2a of hydrogen bonds group.Toluene is added in compound 2a, will be reacted Container is cooled to 5 DEG C, and cyclopentadiene is added dropwise in low temperature, keeps compound 2a and cyclopentadiene molar ratio is 10:13.It is added dropwise After be warming up to reflux temperature and continue to be stirred to react, obtain the norbornene derivative 2b of hydrogen bonds group.Repeat above-mentioned step Suddenly, compound 2a is replaced with allyl alcohol, obtains the norbornene derivative 2c of hydroxyl.By the 11- bromine of 2c and equimolar equivalent Undecanoic acid reacts under the catalysis of DCC and DMAP, obtains the norbornene derivative 2d of bromine atom.30 molar equivalents are hydrogeneous The norbornene derivative 2b of key group, 55 molar equivalent norbornene and 15 molar equivalent 2d are in Grubbs bis- generations catalyst It is reacted in methylene chloride under catalysis, obtains the line style polynorbornene of hydrogen bond group containing side and bromine atom.
Certain gained gained copolymer, 1,10-, 11 carbon diine and phenylazide are taken, bromine atom, 1,10- in copolymer are kept The molar ratio of 11 carbon diines and phenylazide is 5:2:4, and above-mentioned raw materials are calculated as 100 mass parts, it is uniform to add 220 mass parts Mixing naphthenic oil and 80 mass parts of carbon black alkane are sufficiently mixed, and are placed in mold, and of the invention move is obtained after 110 DEG C of heat preservation moldings State polymeric plasticizer swell gel.This material is suitble to require the application of high-intensitive energy-absorbing material, such as bumper outside automobile, energy Enough protection automobile and interior drivers, passenger preferably in traffic accident shock；It is also used as such as car damping piece, noise reduction tooth Wheel, soundproof plate etc., for damping, impact resistance, the sound insulation in use process, and resilience is good, and set resistant is small.
Embodiment 3
A kind of dynamic aggregation object foam based on polyurethane is prepared for energy-absorbing, supermolecular mechanism therein is based on side urea groups With backbone amino formic acid ester group.
The ethyl isocyanate of 2- amino-1,3-propanediol and equimolar equivalent is reacted, the binary containing side urea groups is obtained Alcohol 3a.
It is that hydroxyl one end is azido by resulting dihydric alcohol 3a, 2,4- hexamethylene diisocyanate (HDI), one end It is the oligoethylene glycol of alkynyl, 1,12- diiodo- dodecane according to molar ratio is 16:30 that oligoethylene glycol, one end, which are hydroxyl one end: 7:7:5 mixing, mixture are denoted as 100 mass parts.Add 50 mass parts montmorillonites, 0.2 mass parts organic silicone oil, 1.5 mass The expandable polymer microballoon of part, 0.1 mass parts dibutyl tin dilaurate (DBTDL), the mixing of 0.1 mass parts triethylenediamine Uniformly, and at room temperature solidify 30 minutes.Solidify 4 hours at 80 DEG C later, 110 DEG C keep the temperature 24 hours again, obtain one kind and contain The dynamic aggregation object foamed material of backbone amino formic acid ester group and side urea groups.Dress is protected using the foamed material as athletes ' body It sets, such as knee-pad, neck guard material, the protection that body is impacted for external force.
Embodiment 4
A kind of dynamic aggregation object flexible foam based on polyureas is prepared for energy-absorbing, supermolecular mechanism therein is based on side ammonia Carbamate base.
1- methyl -4- the amino-1,2,3-triazole of equimolar equivalent is sufficiently reacted at 110 DEG C with 6- bromine hexylamine, is obtained To the binary ammonia containing dynamic covalent bond.
Under nitrogen protection, by 10 molar equivalent ethylene glycol monoallyl ethers (average molecular weight about 500) and 1 molar equivalent Potassium methoxide is blended, and the epoxy prapanol of 70 molar equivalents is slowly added dropwise at 95 DEG C, and obtaining end group is the alkene that hydroxyl has branched structure Hydrocarbon monomer 4a.It under nitrogen protection, is olefinic monomer 4a and and hydroxyl molar equivalent of the hydroxyl with branched structure by end group Ethyl isocyanate reacts in methylene chloride under the catalysis of DBTDL, obtains olefinic monomer 4b.By olefinic monomer 4b and 2,4- bis- Amino -6- mercaptopyrimidine equimolar equivalent is sufficiently blended, addition 1wt% photoinitiator 2,2- dimethoxy -2- phenyl acetophenone, Illumination 30 minutes under 300W ultraviolet lamp obtain having the two of cladodification pendant polyether group and cladodification side group end amido-containing acid ester base Ammonia.
X=direct key,
The above-mentioned diamine with hydrogen bond group of 5 molar equivalents, 5 molar equivalent polyethers diaminos, 9 molar equivalents are contained There are the diamino, 20 molar equivalent toluene di-isocyanate(TDI)s, 2 molar equivalent 6- bromine hexylamines of dynamic covalent bond to be blended, is calculated as 100 mass Part, add 1 mass of water-soluble organic silicone oil, 2 mass parts water, 0.2 mass parts DBTDL, 0.1 mass parts triethylene two Amine, is uniformly mixed and quickly stirring solidifies 15 minutes at room temperature to bubble is generated, and solidifies 2 hours at 60 DEG C then to get arriving Dynamic aggregation object foamed product of the invention.The light softness of the product, can be used as back cushion with damping, buffering function, headrest, The filler of pillow etc. is also suitable for the energy-absorbing application of human body, precision instrument, breakables protection etc., facilitates personal/fitting It uses.
Embodiment 5
A kind of dynamic aggregation object ordinary solid based on polyethers is prepared, supermolecular mechanism therein is based on side piperidyl, side Pyrazinyl and side imidazolyl.
By equimolar equivalent 11- bromine undecanoic acid and 5- ethyl -1- phenyl -1H- [1,2,3] triazole -4- formic acid at 110 DEG C Sufficiently reaction, obtains the diacid containing dynamic covalent bond in skeleton.By resulting diacid and polyethylene glycol diepoxide for example methyl Ether is mixed according to molar ratio 5:3:2, and a kind of polymer containing pendant hydroxyl group is prepared.By resulting polymers, 4- piperidinecarboxylic acid, 2- formic acid pyrazine, imidazoles -4- acetic acid press pendant hydroxyl group, 4- piperidinecarboxylic acid, 2- formic acid pyrazine, imidazoles -4- acetic acid, 4- bromo-butyric acid mole It is sufficiently blended than 7:2:1:2:1, under the catalysis of DCC and DMAP, obtains the dynamic aggregation object of the hydrogen bond group containing side.
It is sufficiently mixed dynamic aggregation object, 5 parts by mass of cellulose obtained by 100 mass parts are nanocrystalline and form to get to phase The dynamic aggregation Tetramune answered.Army and police's protective article, explosion-proof layer etc. is made with good impact resistance with the material, is used for To the snubber of extraneous impact force such as explosion wave.
Embodiment 6
A kind of dynamic aggregation object ionic liquid gel based on polyethers is prepared for energy-absorbing, supermolecular mechanism therein is based on Side urea groups.
The ethyl isocyanate of 2- amino -3- sulfydryl -1- propyl alcohol and equimolar equivalent is reacted, converts urea groups for amino. Gained compound is first reacted under ultraviolet lighting in the presence of photoinitiator b DK with the bromo- 1- butylene of equimolar equivalent 4-, then It is reacted under the catalysis of triethylamine with 1-ten polyethylene glycol of molar equivalent nitrine-acyl chlorides, it is folded that obtain one end, which be bromine atom one end, Nitrogen base side group is the modified polyether of urea groups.Gained modified polyether and propine is anti-in 35 DEG C under the catalysis of cuprous iodide and pyridine Answer, obtain one end be triazolyl one end be bromine atom and contain a side urea groups modified polyether.
By 1 molar equivalent 1,6- dibromo-hexane, (bromomethyl) benzene of 1,3,5- tri- and the resulting modified polyether of 50 molar equivalents It is blended, and in 110 DEG C of sufficiently reactions, obtains dynamic aggregation object of the invention.By dynamic aggregation object and 100 obtained by 100 mass parts Mass parts ionic liquid 1-butyl-3-methyl imidazolium bis trifluoromethyl sulfimide salt ([bmim] NTf2) is sufficiently mixed Obtain dynamic aggregation object ionic liquid gel of the invention.
The resulting ionic liquid gel of the present embodiment can be used as the squeegee of compound glass and multi-layered board, for shellproof and It is explosion-proof etc..
Embodiment 7
A kind of dynamic aggregation object foam based on polyester is prepared for energy-absorbing, supermolecular mechanism therein is based on end amide Base.
Under anhydrous condition, using 1 molar equivalent cyclodextrin as initiator, using stannous octoate as catalyst, by 210 molar equivalents 6-caprolactone is dissolved in toluene and carries out cyclic esters ring-opening polymerization, obtains 21 hydroxy-end capped arm polyester.By 21 molar equivalent 4- bromines Butyl chloride and gained polyester react under the catalysis of triethylamine, obtain the 21 arm polyester blocked by bromine atom.
Under anhydrous condition, using N- acetyl ethanonlamine as initiator, using stannous octoate as catalyst, by 10 molar equivalent ε-oneself Lactone is dissolved in toluene and carries out cyclic esters ring-opening polymerization, and obtaining one end is the oligoester that amide groups is contained in hydroxyl one end.Gained is oligomeric Ester reacts under the catalysis of triethylamine with the 5- hexin acyl chlorides of equimolar equivalent, and obtaining one end is that amide groups is contained in alkynyl one end Oligoester.The resulting oligoester of 15 molar equivalents, 15 molar equivalent ethyl azidoacetates and 1 molar equivalent are blocked by bromine atom 21 arm polyester blends and be heated to 110 DEG C and keep the temperature 48 hours after swell in 1,4- dioxane solvent.Solvent will be contained Blend be placed in mold and freezed completely at -80 DEG C, open aspiration pump at -50 DEG C, maintain dry air pressure less than 50 μ It is atm24 hours, dry in 20 DEG C of vacuum ovens, whole solvents are extracted, dynamic aggregation object foam material of the invention is obtained Material.Protective package packing material is made with the material, is used for bumper and absorbing shock, is also used as the use of protectiveness carrier.
Embodiment 8
A kind of dynamic aggregation object based on polyethers is prepared for energy-absorbing, supermolecular mechanism therein is based on end diamino triazine Base and end thymine base.
Using BDK as photoinitiator, by 2- vinyl -4,6- bis- of 1 molar equivalent 3- bromo- 1- propanethiol and 1 molar equivalent Amino -1,3,5-triazines reacts under ultraviolet lighting, and obtaining one end is the compound that hydrogen bond group one end is bromine atom.With BDK It is vinyl -4 2- that sulfydryl one end is azido polyethylene glycol and 1 molar equivalent by 1 molar equivalent one end for photoinitiator, 6- diamino-1,3,5-triazines reacts under ultraviolet lighting, and obtaining one end is the polyethylene glycol that hydrogen bond group one end is azido. The resulting polyethylene glycol of 1 molar equivalent is reacted with the heating of the 4- acetylenylbenzene methyl ether of equimolar equivalent, obtaining one end is hydrogen bond Contain the polyethylene glycol of triazolyl in group one end.Using BDK as photoinitiator, the poly- second of four arms that 1 molar equivalent is blocked with sulfydryl Two pure and mild 4 molar equivalent 1- (4- vinyl benzene methyl) thymidines are reacted under ultraviolet lighting, obtain being blocked with thymidine Four arm polyethylene glycol.By 10 molar equivalent one end be hydrogen bond group one end be the compound of bromine atom, 8 molar equivalent one end are Contain the polyethylene glycol of triazolyl and four arm polyethylene glycol and the total matter of 9 molar equivalent thymidines sealing end in hydrogen bond group one end The graphene of amount 5% is sufficiently blended, and sufficiently reaction obtains dynamic aggregation object of the invention at 110 DEG C.With the dynamic aggregation object As filler, it can apply to use on textile or in foams, have the function of bumper and absorbing shock, can also have electricity Sensing function.
Embodiment 9
A kind of dynamic aggregation object ionic liquid gel based on polyacrylate and polyacrylonitrile is prepared for energy-absorbing, wherein Supermolecular mechanism be based on side carbamateyl and side urea groups.
By acrylonitrile (average molecular weight about 10000) 1 molar equivalent, 3 molar equivalent of 2- azido second ammonia, 2,5- dehydrations- 20 molar equivalent of 1- nitrine -1- deoxy-D-glucose alcohol, 100 molar equivalent of zinc chloride are dissolved in dimethylformamide, surpass at room temperature 125 DEG C are warming up to after enabling each component be sufficiently mixed within sound 5 minutes to be stirred to react, and obtain the modified polypropene of side group hydroxyl and amino Nitrile.By resulting modified polyacrylonitrile and with the ethyl isocyanate of the sum of contained hydroxyl amino equimolar equivalent in dimethyl sulfoxide Middle reaction obtains the modified polyacrylonitrile of side group amido-containing acid ester and urea groups.
By 1- phenyl -4- methanol-based -1H-1,2,3- triazoles and acryloyl chloride react under the catalysis of triethylamine, obtain band There is the acrylate monomer of triazolyl.The bromo- 2- propyl alcohol of 1,3- bis- and acryloyl chloride are reacted under the catalysis of triethylamine, obtain band There is the acrylate monomer of bromine atom.50 molar equivalent butyl acrylates, 20 molar equivalents are had to the acrylate of triazolyl Monomer, 15 molar equivalents have the acrylate monomer and 1 molar equivalent photoinitiator 2- hydroxy-2-methyl -1- benzene of bromine atom After base -1- acetone sufficiently reacts in the UV lamp, the polyacrylate with triazole side group and bromine atom is obtained.
The resulting side group amido-containing acid ester of 100 mass parts and the modified polyacrylonitrile of urea bond, 100 mass parts is resulting Polyacrylate and 200 mass parts 1- butyl -2,3- methylimidazole tetrafluoroborates, 20 mass parts carbon nanotubes with it is suitable Solvent dimethylformamide removes solvent after 110 DEG C of heating sufficiently reaction after being sufficiently mixed again, obtains corresponding dynamic aggregation Object ionic liquid gel.The ionic liquid gel of embodiment preparation can be used as the squeegee with damping shock absorption function, block Glue, and there is good heating effect under near infrared light.
Embodiment 10
A kind of dynamic aggregation object plasticizer swell gel based on polyvinyl chloride is prepared for energy-absorbing, supermolecule therein is made With based on side urea groups.
Branching type polyvinyl chloride (average molecular weight about 50000) and 4- (2- pyrrolidinyl) benzenethiol are dissolved in hexamethylene and existed 60 DEG C are reacted 12 hours, and keeping the molar ratio of side group chlorine atom and 4- (2- pyrrolidinyl) benzenethiol is about 3:2, are obtained containing side The polyvinyl chloride of secondary amino group.By in side group containing parahelium polyvinyl chloride and methyl isocyanate react in methylene chloride, keep The molar ratio of secondary amino group and methyl isocyanate is about 1:1, obtains side group containing the polyvinyl chloride for replacing urea groups.
Branching type polyvinyl chloride and sodium azide are reacted in hexamethylene in 60 DEG C, convert part side group chlorine atom to Azido.The bromo- 2- butanol of the Isosorbide-5-Nitrae-two of equimolar equivalent and 5- hexin acyl chlorides are reacted under the catalysis of triethylamine, obtain chemical combination Object 10a.
Taking a certain amount of part side group is polyvinyl chloride, the positive pentyne of compound 10a, 5- bromine of azido, keeps azido, changes The molar ratio for closing the positive pentyne of object 10a, 5- bromine is 5:3:2, and mixture is calculated as 100 mass parts, adds and contains obtained by 100 mass parts Have the polyvinyl chloride, 70 mass parts epoxidized soybean oils, 50 mass parts tricresyl phosphates of side hydrogen bond group, after mixing in Sufficiently reaction forms to get dynamic aggregation object plasticizer swell gel of the invention is arrived at 110 DEG C.Using the material as buffering Plate, buffer strip etc., for providing excellent shock resistance.
11 crosslinked polyacrylate of embodiment, polyacrylate side chain contain thiocarbamate base in side chain；End group For the branched polyethylene imine of urea groups
A kind of dynamic aggregation object ionic liquid gel based on polyacrylate and polyethyleneimine is prepared for energy-absorbing, In supermolecular mechanism be based on side thiocarbamate base and end urea groups.
[1- (phenyl methyl) -1,2,3-triazoles -4- base] methanol and acryloyl chloride are reacted under the catalysis of triethylamine, obtained To the acrylate monomer for having triazolyl.3- iodine propyl alcohol and acryloyl chloride are reacted under the catalysis of triethylamine, had The acrylate monomer of iodine atom.Under the conditions of anhydrous and oxygen-free, by the isocyanates ethyl acrylate of ethyl mercaptan and equimolar equivalent It is reacted in methylene chloride under triethylamine catalysis, obtains the acrylate monomer containing thio carbamate groups.
Under the conditions of anhydrous and oxygen-free, initiator 2 bromopropionic acid methyl esters and the acrylate containing thio carbamate groups are kept The molar ratio of monomer be 1:15, under the catalysis of cuprous bromide and PMDETA, in 70 DEG C polymerize, reaction obtain side group contain it is thio The polyacrylate of carbamate groups.Polyacrylate obtained by 1 molar equivalent and 25 molar equivalent 5- amino -1- amylalcohols is molten In DMSO, reacted 30 minutes in 40 DEG C.Reaction solution is instilled into methylene chloride, with hydrochloric acid, sodium bicarbonate solution and water washing, through nothing The polymer that one end is hydroxyl is obtained after water magnesium sulfate is dry.Resulting polymers and acryloyl chloride are anti-under the catalysis of triethylamine It answers, obtains the esters of acrylic acid macromonomer containing hydrogen bond group.
The isophorone diisocyanate of equimolar equivalent and n-propylamine are dissolved in DMF, are added after complete reaction certain The branched polyethylene imine (average molecular weight is about 20000) of amount, and keep in polyethyleneimine segment middle-end amino and solution Isocyanate group be 3:2, obtain end group be urea groups modified branched polyethylene imines.Take the 30 positive fourths of molar equivalent acrylic acid Ester, 10 molar equivalents have the acrylate monomer of triazolyl, and 20 molar equivalents have the acrylate monomer and 5 of iodine atom Molar equivalent contains the esters of acrylic acid macromonomer of hydrogen bond group, is calculated as 100 mass parts, with 1 molar equivalent photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone, 50 mass parts modified branched polyethylene imines, 150 mass parts ionic liquid 1- fourths It is sufficiently mixed in base -3- methylimidazole hexafluorophosphate, and the quality of ionic liquid is the 50% of mixture total weight.In ultraviolet lamp Lower illumination reaction stopped illumination after 4 hours, after being heated to 110 DEG C of abundant reactions, obtained dynamic aggregation object ionic liquid of the invention Body gel.The ionic liquid gel of embodiment preparation can be used as the squeegee with damping shock absorption function, block glue.
Embodiment 12
A kind of dynamic aggregation object foam based on ethylene-butylene random copolymer and polyethylene is prepared for energy-absorbing, In supermolecular mechanism be based on triazoline diketone-ene adducts side group and side urea groups pyrimidine ketone group.
Under anhydrous condition, the toluene of reactor volume 14% is added in reactor and 1 atmospheric pressure of maintenance by ethylene full of 2L And the butadiene toluene solution (9wt%) of volume 0.95%.It is added in 40 DEG C and contains scandium catalyst, AliBu3[Ph3C][B (C6F5)4] 20 milliliters of catalyst solution, meanwhile, the butadiene first of reactor volume 6% is instilled with 6 milliliters of speed per minute Benzole soln (9wt%).After butadiene solution is all added dropwise, 20 milliliters of acidified methanols are rapidly added, and product is sunk in ethanol It forms sediment, obtains ethylene-butylene random copolymer.
Gained copolymer is reacted under the initiation of azo-bis-isobutyl cyanide in 60 DEG C with a certain amount of thioacetic acid, is kept altogether The molar ratio of alkenyl and thioacetic acid in polymers is 10:1, obtains the ethylene-butylene random copolymer that side group has carboxyl. By gained copolymer and the iodo- 2- propyl alcohol of a certain amount of 1,3- bis- and 1- phenyl -4- methanol-based -1H-1,2,3- triazole in DCC and It is reacted under the catalysis of DMAP, keeps side carboxyl, the iodo- 2- propyl alcohol of 1,3- bis- and 1- phenyl -4- methanol-based -1H-1 in copolymer, 2, The molar ratio of 3- triazole is 5:2:3, obtains the ethylene-butylene random copolymer that side group contains bromine atom and triazole.By gained Copolymer and a certain amount of 4- methyl-1,2,4- triazoline -3,5- diketone are dissolved in tetrahydrofuran, keep double bond and 4- methyl-1, and 2, The molar ratio of 4- triazoline -3,5- diketone is 5:1, is sufficiently reacted after stirring, obtains side group and contains hydrogen bond group and bromine atom Ethene improved-butadiene random copolymer.
Low-density cladodification polyethylene (average molecular weight is about 20000) is dissolved by heating in dimethylbenzene, 100 moles is added and works as The initiator cumyl peroxide for being dissolved in dimethylbenzene, constant temperature is added after solution temperature rises to 130 DEG C in the maleic anhydride of amount Reaction obtained Research of Grafting Malaic Anhydride Onto Polyethylene after 1 to 3 hour.Under inert gas protection, UPy derivative 12a and gained are gathered Vinyl Graft maleic anhydride is dissolved in dimethylbenzene, and keeping the molar ratio of compound 12a and maleic anhydride side group is 1:1, and stirring is lower to be added Enter catalyst paratoluenesulfonic acid sodium salt, is stirred to react in 105 DEG C.By water in the dichloromethane solution of products therefrom and trifluoroacetic acid Solution, obtains the modified poly ethylene containing UPy side group hydrogen bond group.
By the resulting ethene improved-butadiene random copolymer of 100 mass parts, the resulting modified poly ethylene of 50 mass parts, The odium stearate of 30 mass parts, 20 mass parts calcium carbonate, 0.2 mass parts antioxidant 754, the sodium bicarbonate of 8 mass parts and 0.2 matter Amount part vaseline oil is sufficiently blended, and extrusion molding obtains corresponding foamed product, and in 110 DEG C of sufficiently solidifications, obtains the present invention Dynamic aggregation object foam.The foam can be used as sole, conveyer belt components etc. for buffering, while have good wear-resisting Property.
Embodiment 13
A kind of dynamic aggregation object elastomer based on polysiloxanes and polyethylene glycol is prepared for energy-absorbing, supermolecule therein Effect is based on end cytimidine base and end guanyl-.
Cytimidine is reacted under the catalysis of triethylamine with the polyethylene glycol that both ends are succinimidyl succinate base, is obtained It is the polyethylene glycol of cytimidine base to both ends.Guanine is existed with both ends for the polyethylene glycol of succinimidyl succinate base It is reacted under the catalysis of triethylamine, obtains the polyethylene glycol that both ends are guanyl-.
By the bromo- 1- hexene of 6- and excessive reaction of sodium azide, 6- azido -1- hexene is obtained.It is catalysis with chloroplatinic acid Agent, by the polysiloxanes containing 3 molar equivalent silicon hydrogen and the bromo- 1- hexene of 2 molar equivalent 6- and 1 molar equivalent 6- azido -1- Hexene reacts 3 hours at 90 DEG C in cyclohexanone, obtains the cross linking polysiloxane containing dynamic covalent bond.
By the resulting polysiloxanes of 100 mass parts, each 50 mass parts of resulting two kinds of polyethylene glycol and a certain amount of one End is that four polyethylene glycol of alkynyl are sufficiently blended, and keeping the molar ratio of azido and alkynyl in mixture is 1:1, at 110 DEG C Sufficiently reaction, obtains dynamic aggregation object elastomer of the invention.With the protective materials dropped from the air and dropped made of the elastomer, use In buffering shock resistance.
Embodiment 14
Prepare the dynamic aggregation object foamed elastic of a kind of styrene-based-butadiene random copolymer rubber and polyisobutene Body is used for energy-absorbing, and supermolecular mechanism therein is based on Amino End Group formic acid ester group and end urea groups.
After 2, the 4- toluene di-isocyanate(TDI) of the amino-terminated polyisobutene in one end and equimolar equivalent is sufficiently reacted, Equimolar eq. ethanol is added, the reaction was continued under the catalysis of TDBDL, obtains the poly- isobutyl of modification that end hydrogen bond group is contained in one end Alkene.
Using BDK as photoinitiator, by a certain amount of line style styrene butadiene random copolymer and the bromo- 1- propanethiol of 3-, - four polyethylene glycol of sulfydryl-nitrine reacts under ultraviolet light, and the double bond in copolymer, the bromo- 1- propanethiol of 3-, sulfydryl-four is kept to gather Ethylene glycol-nitrine molar ratio is 15:3:2, obtains the copolymer that side group contains bromine atom and azido.By gained copolymer with 4- toluene ethyl-acetylene is under the catalysis of cuprous iodide and pyridine, and reaction obtains side group and contains bromine atom and triazolyl at 35 DEG C Copolymer.
By resulting 40 mass parts of modification polyisobutene containing end hydrogen bond group, 25 mass parts of polystyrene, poly-vinegar acid 8 mass parts of vinyl acetate, resulting side group contain 100 mass parts of styrene butadiene random copolymer of bromine atom and triazolyl Mold is filled this blend into, is set after being down to 60 DEG C, heat preservation 1 hour to temperature in 110-120 DEG C of melting and abundant blending reaction In pressure reaction still, it is passed through supersaturated carbon dioxide, is heated to 90 DEG C, pressure control is after 7-14MPa, 4 hours with per second The speed of 1MPa is depressured, and product is cooling in ice water rapidly, and dynamic aggregation compositions foam of the invention is obtained after demoulding Product.The foamed product can be used for damping, while also act as light heat-insulating material.
Embodiment 15
Prepare a kind of dynamic aggregation object water-setting based on polyvinyl acetate-polyvinyl alcohol random copolymer and polyethylene glycol Glue is used for energy-absorbing, and supermolecular mechanism therein is based on side oxygen thia oxazolidinyl, end diamides base naphthyridines base and end urea groups pyrimidone Base.
By a certain amount of polyvinyl acetate-polyvinyl alcohol random copolymer, (average molecular weight is about 10000, alcoholysis degree About 20%), 5- bromine valeric acid, 5- ethyl -1- phenyl -1H- [1,2,3] triazole -4- formic acid, the third cysteine are dissolved in tetrahydro furan It mutters, keeps hydroxyl, 5- bromine valeric acid, 5- ethyl -1- phenyl -1H- [1,2,3] triazole -4- formic acid, the third cysteine in copolymer Molar ratio is 10:4:3:3, under the catalysis of bicyclic ethyl carbodiimide (DCC) and 4-dimethylaminopyridine (DMAP), is contained There is the modified polyvinyl acetate of side group bromine atom, side triazolyl and side oxygen thia oxazolidinyl.
Using methylene chloride as solvent, the polyethylene glycol that both ends acid chloride end groups block is reacted with ammonium hydroxide, obtains both ends Base is the polyethylene glycol of amide groups.It is catalysis with lead acetate, the bis- diphenylphosphine -9,9- xanthphos of 4,5- and potassium carbonate Agent, by 10 molar equivalents 2, chloro- 1, the 8- naphthyridines of 7- bis- reacts in chloroform with 9 molar equivalent 2- ethyl hexanoyl ammonia, obtains one end The naphthyridines intermediate being connected with 2- ethyl hexanoyl amino.It is amide groups by the resulting naphthyridines intermediate of 2 molar equivalents and two end groups Polyethylene glycol reacted under the catalysis of lead acetate, bis- diphenylphosphine -9, the 9- xanthphos of 4,5- and potassium carbonate, obtain two Hold the polycyclic octene containing 2,7- amide groups -1,8- naphthyridines end group.In anhydrous conditions, by 1 molar equivalent compound 15a and 1 Molar equivalent 2,6- diisopropyl phenylisocyanate are dissolved in tetrahydrofuran, react 16 hours at room temperature, and obtaining one end is alkenyl UPy derivative 15b.Being total in BDK and ultraviolet light with the mercaptoethanol of equimolar equivalent respectively by gained UPy derivative 15b It is reacted under same-action, converts hydroxyl for alkenyl, obtain the UPy derivative 15c that one end is hydroxyl.It is by 2 molar equivalent one end The UPy derivative 15c and 1 molar equivalent, two end group of hydroxyl are that the polyethylene glycol of carboxyl reacts under the catalysis of DCC and DMAP, are obtained Contain the polyethylene glycol of UPy derivative base to both ends.
By 100 mass parts contain side group bromine atom, side triazolyl and side oxygen thia oxazolidinyl modified polyvinyl acetate, The polyethylene glycol and 30 mass parts both ends that 2,7- amide groups -1,8- naphthyridines end group is contained at 20 mass parts both ends contain UPy derivative The polyethylene glycol of base is sufficiently mixed, and is swollen in water after sufficiently reacting at 110 DEG C, is obtained dynamic aggregation object water-setting of the invention Glue.The packaging packing material that the resulting hydrogel of the present embodiment can be used as protecting against shock uses.
Embodiment 16
A kind of dynamic aggregation object elastomer based on polysiloxanes and poly-β-hybroxybutyric acid is prepared for energy-absorbing, it is therein Supermolecular mechanism is based on side imidazoline ketone group, framework amide base and end urea groups pyrimidine ketone group.
By the high molecular weight poly-β-hybroxybutyric acid of 1 molar equivalent, (300000) PHB, average molecular weight are about dissolved in dichloromethane Alkane instills the mixed solution for containing 1000 molar equivalent p-methyl benzenesulfonic acid and 10000 molar equivalent 1,4-butanediol.It is anti-at room temperature It answers, with methanol extraction and rinses product, obtaining the low molecular weight poly-β-hybroxybutyric acid that both ends are hydroxyl, (average molecular weight is about 3000).By UPy derivative 18c that one end is alkenyl respectively with the thioacetic acid of equimolar equivalent in the common of BDK and ultraviolet light The lower reaction of effect, converts carboxyl for alkenyl.By the PHB and 2 molar equivalent carboxyls envelope that the resulting both ends of 1 molar equivalent are hydroxyl The UPy derivative at end reacts under the catalysis of DCC and DMAP, obtains the PHB that two end groups are UPy derivative.
Under nitrogen protection, amination dimethyl siloxane 16a is added in urea, keeps the molar ratio of urea and side amino It is down to room temperature, obtains the ketone group of imidazoline containing side and side ammonia after being to slowly warm up to 160 DEG C, heat preservation about 1 hour under stirring for 9:10 The modified dimethyl polysiloxane 16b of base.
By a certain amount of modified dimethyl polysiloxane 16b and 5- bromine valeric acid, 5- ethyl -1- phenyl -1H- [1,2,3] triazole - 4- formic acid is blended, and keeps side amino and 5- bromine valeric acid, 5- ethyl -1- phenyl -1H- [1,2,3] triazole-in dimethyl silicone polymer The molar ratio of 4- formic acid is 5:3:2, is carried out in the presence of condensing agent 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline Acylation reaction obtains the dimethyl silicone polymer that side group contains bromine atom, triazolyl and hydrogen bond group.By resulting modification poly- two 100 mass parts of methylsiloxane are that UPy derivative PHB is blended with the resulting both ends of 50 mass parts, in 110 DEG C of sufficiently reactions, are obtained To dynamic aggregation object of the invention.
The sealing element of component using this dynamic aggregation object as electronic product, has protecting against shock function again while waterproof Can,
Embodiment 17
A kind of dynamic aggregation object elastomer based on polyisobutene and polyacrylate is prepared for energy-absorbing, oversubscription therein Son effect is based on side urea groups.
Acrylic acid 2- amino-ethyl ester and 4- biphenyl isocyanates are reacted in methylene chloride, keep amino and different The molar ratio of cyanate is 1:1, obtains the acrylate monomer 17a containing urea groups.By isocyanates ethyl acrylate and n-propylamine It is reacted in methylene chloride, keeping the molar ratio of amino and isocyanates is 1:1, obtains the acrylate monomer containing urea groups 17b.Isocyanates ethyl acrylate and nafoxidine are reacted in methylene chloride, keep rubbing for isocyanates and amino You obtain the acrylate monomer 17c of the derivative containing urea bond than being 1:1.By 1 molar equivalent photoinitiator 2- hydroxy-2-methyl- 1- phenyl -1- acetone, 10 molar equivalent 17a, 30 molar equivalent 17b, 10 molar equivalent 17c, 10 molar equivalent methacrylic acids Ethyl ester is sufficiently blended to be polymerize under light illumination, obtains poly- (methyl) acrylate of the modification containing not ipsilateral urea groups.
By the hydroxy-end capped polyisobutene in 4 molar equivalent both ends and 3 molar equivalent 1- benzyl -1,2,3- triazole -4,5- two Carboxylic acid reacts under the catalysis of DCC and DMAP, and excessive n-butyric acie is added after carboxylic acid reaction is complete, and the reaction was continued, obtains containing three The polyisobutene of oxazolyl.
Modified poly- (methyl) acrylate obtained by 30 mass parts is broken into particle, with the resulting poly- isobutyl of 100 mass parts Alkene and bis- iodohexane of a certain amount of 1,6- keep the molar ratio of triazolyl and iodine atom in polyisobutene in 110 DEG C of sufficiently reactions For 3:4, dynamic aggregation object elastomer of the invention is obtained.In the present embodiment, gained elastomer can be used as packaging material, play slow Suction the purpose of energy.
Embodiment 18
A kind of dynamic aggregation object oligomer swell gel based on polyethers is prepared for energy-absorbing, supermolecular mechanism base therein In Amino End Group formic acid ester group.
Under nitrogen protection, 5 molar equivalent pentaerythrites and 2 molar equivalent potassium methoxides are blended, are slowly added dropwise at 95 DEG C The epoxy prapanol of 300 molar equivalents, it is the polyethers of hydroxyl that obtaining, which has dissaving structure end group,.By gained polyethers with it is excessive different Ethyl cyanate reacts under the catalysis of DBTDL, and after complete reaction, it is carbamate that obtaining, which has dissaving structure end group, Polyethers.
3-three polyethylene glycol of molar equivalent nitrine-propargyl and 4-seven polyethylene glycol of molar equivalent bromo-bromo is abundant It is blended, the weighing of gained mixture is calculated as 100 mass parts, adds hyperbranched polyether, 100 mass parts alkyl obtained by 50 mass parts The polyethylene glycol oligomer of sealing end reacts in 110 DEG C, obtains dynamic aggregation object oligomer swell gel of the invention.
The oligomer swell gel can be used as buffer interlayer, and it is shock proof to play the role of buffering.
Embodiment 19
Dynamic aggregation object elastomer of the one kind based on poly- (2- oxazolidine) and polythiaether is prepared for energy-absorbing, oversubscription therein Son effect is based on side benzimidazole, framework amide base and side oxazolidine ketone group.
The Isosorbide-5-Nitrae of equimolar equivalent-pentadiene -3- alcohol and 5- chloromethyl -2- oxazolidone are dissolved in toluene, are with potassium carbonate Catalyst obtains the diene containing side oxazolidine ketone group using tetrabutylammonium bromide as consisting of phase-transferring agent.By the 1,4- of equimolar equivalent The diene and suitable benzoin dimethylether photoinitiator that succinimide mercaptans, 4 molar equivalents contain side oxazolidine ketone group are blended, in purple Illumination reaction under outer lamp obtains the polythiaether containing side hydrogen bond group.
Using 1 molar equivalent p-methyl benzenesulfonic acid propynyl ester as initiator, 1 molar equivalent hexynic acid is terminator, carries out 20 and rubs The cation ring-opening polymerization of your equivalent 2- (3- ethylheptyl) -2- oxazoline, obtains poly- (the 2- oxazole that both ends are blocked with alkynyl Quinoline).Pure and mild benzimidazole -5- the formic acid of the Isosorbide-5-Nitrae of equimolar equivalent-pentadiine -3- is reacted under the catalysis of DCC and DMAP, is obtained To the diine containing side benzimidazolyl.By the 6- heptynoic acid of equimolar equivalent and propargylamine in condensing agent 2- ethyoxyl -1- Acylation reaction is carried out in the presence of ethoxy carbonic acyl radical -1,2- dihydroquinoline, obtains the diine containing framework amide base.
Side benzimidazolyl is contained into poly- (2- oxazoline), 10 molar equivalents that alkynyl blocks in 35 molar equivalent both ends Diine, 5 molar equivalents contain the diine of framework amide base, 49 molar equivalent 1,11- diazido -3,6,9- trioxas 11 Alkane, 35 molar equivalents 1,8- diiodo-octane are blended, and are calculated as 100 mass parts, add 30 mass parts and contain the poly- of side hydrogen bond group Thioether sufficiently reacts at 110 DEG C after being sufficiently blended, and obtains dynamic aggregation object elastomer of the invention.With this dynamic aggregation object Each type component, plays the role of bumper and absorbing shock made of elastomer.
Embodiment 20
A kind of dynamic aggregation object foam based on poly- limonene carbonic ester and poly-β-hybroxybutyric acid is prepared for energy-absorbing, In supermolecular mechanism be based on side urea groups pyrimidine ketone group and side carbamateyl.
Under the conditions of 90 DEG C of anhydrous no air, limonene oxide and catalyst 20a are dissolved in toluene, keep limonene oxide Molar ratio with catalyst is 100:1, and 10bar carbon dioxide is passed through into reaction vessel, and reaction obtains poly- limonene carbonic ester 23b.A certain amount of resulting poly- limonene carbonic ester 20b is dissolved in chloroform, excess 2- thioacetic acid, the positive fourth of 3- mercaptopropionic acid is added Ester and azo-bis-isobutyl cyanide, keeping 2- thioacetic acid, 3- mercaptopropionic acid N-butyl, the molar ratio of initiator is 3:7:3, at 60 DEG C Lower reaction obtains the poly- limonene carbonic ester that part side group is carboxyl.It is the poly- limonene carbonic acid of carboxyl by resulting part side group Ester, the iodo- 1- hexanol of UPy derivative 15c, 6-, the 1- phenyl -4- methanol-based -1H-1 that one end is hydroxyl, 2,3- triazoles are blended, protect Hold side carboxyl in poly- limonene carbonic ester, one end is the iodo- 1- hexanol of UPy derivative, 6- of hydroxyl, 1- phenyl -4- methanol-based - The molar ratio of 1H-1,2,3- triazoles are 10:3:4:3, and the pyrimidine of urea groups containing side ketone group, iodine atom and triazolyl are obtained after fully reacting The poly- limonene carbonic ester of modification.
6- amino -1- hexanol and methylchloroformate are reacted in methylene chloride, using anhydrous sodium bicarbonate as catalyst, control The molal quantity ratio of amino and methylchloroformate processed is 10:11, obtains compound 20c.By poly-β-hybroxybutyric acid (mean molecule Amount about 20000) and maleic anhydride be dissolved in chlorobenzene, make the initial mass volumetric concentration 3% of maleic anhydride.It was added at 130 DEG C Benzoyl Oxide makes the initial concentration 0.2% of benzoyl peroxide, is kept for thermotonus 6 hours, obtains Poly-β-hydroxybutyric acid Ester grafted maleic anhydride.Under inert gas protection, poly-β-hybroxybutyric acid grafted maleic anhydride and compound 20c are dissolved in two Toluene, keeps maleic anhydride side group and the molar ratio of compound segment 20c is 1:2.1.Catalyst is added with stirring to toluene sulphur Sour sodium is stirred to react in 105 DEG C, obtains the modification poly-β-hybroxybutyric acid in side group containing urethane bond.
By 100 mass parts resulting cross-linking modified poly- limonene carbonic esters, 50 mass parts containing urethane bond Modified poly-β-hybroxybutyric acid, the polyester tiny balloon of 50 mass parts and 15 mass parts polyvinylpyrrolidone microballoons are sufficiently mixed Afterwards in 110 DEG C of sufficiently reactions, dynamic aggregation object foam of the invention is obtained.
The dynamic aggregation compositions primary raw material is renewable raw materials, is widely used as non-returnable container material, is used for Damping protection, while there is certain moisture pick-up properties.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (10)

1. a kind of energy-absorbing method based on dynamic aggregation object, which is characterized in that provide a kind of dynamic aggregation object and using it as inhaling Energy material carries out energy-absorbing, wherein containing at least one cross-linked network in the dynamic aggregation object, and simultaneously containing based on alkyl The commutative covalent bond of triazole and the halogenated alkyl reacted can be swapped with alkyl triazole；Wherein, described based on alkane The commutative covalent bond of base triazole has structure shown in following formula formula (1):
Wherein, X—For anion, it is selected from bromide ion, iodide ion；It indicates and polymer chain or any other suitable base The connection of group/atom；
Wherein, the halogenated alkyl reacted that can swap with the commutative covalent bond based on alkyl triazole has following formula Structure shown in formula (2):
Wherein, X is halogen atom, is selected from bromine atom, iodine atom；Wherein,Expression and polymer chain are any other suitable Group or atom connection.
2. a kind of energy-absorbing method based on dynamic aggregation object according to claim 1, which is characterized in that dynamic described in wherein Also containing the hydrogen bond group that can form supermolecule hydrogen bond action in state polymer.
3. a kind of energy-absorbing method based on dynamic aggregation object according to claim 2, which is characterized in that dynamic described in wherein State polymer has one of network structure as described below:
Only one cross-linked network in the dynamic aggregation object contains dynamic covalent cross-linking and oversubscription in the cross-linked network simultaneously Son crosslinking, wherein the degree of cross linking of dynamic covalent cross-linking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point Above and below；
Only one cross-linked network in the dynamic aggregation object contains dynamic covalent cross-linking and oversubscription in the cross-linked network simultaneously Son crosslinking, wherein the degree of cross linking of dynamic covalent cross-linking in its gel point hereinafter, supermolecule crosslinking the degree of cross linking its gel point with On；
Only one cross-linked network in the dynamic aggregation object contains dynamic covalent cross-linking and oversubscription in the cross-linked network simultaneously Son crosslinking, wherein the degree of cross linking of dynamic covalent cross-linking in its gel point hereinafter, supermolecule crosslinking the degree of cross linking its gel point with Under, but the sum of the two degree of cross linking is more than gel point；
Containing there are two networks in the dynamic aggregation object；Dynamic covalent cross-linking is contained only in 1st network, the degree of cross linking is in its gel Or more；Supermolecule crosslinking is contained only in 2nd network, the degree of cross linking is more than its gel point；
Containing there are two networks in the dynamic aggregation object；Covalent cross-linking containing dynamic and supermolecule crosslinking, the crosslinking in 1st network Be crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in network, wherein the degree of cross linking of dynamic covalent cross-linking its gel point with On, the degree of cross linking of supermolecule crosslinking is in its gel point above and below；Supermolecule crosslinking is contained only in 2nd network, the degree of cross linking exists It is more than its gel point；
Contain a network in the dynamic aggregation object, wherein only containing dynamic covalent cross-linking more than gel point, supermolecule The degree of cross linking is dispersed in dynamic covalent cross-linking network in its gel point supermolecule polymer below；
Contain a network in the dynamic aggregation object, is handed over simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network Connection, wherein the degree of cross linking of dynamic covalent cross-linking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is more than its gel point Or it is following；The supermolecule degree of cross linking is dispersed in dynamic covalent cross-linking network in its gel point supermolecule polymer below；
Contain a network in the dynamic aggregation object, wherein only containing dynamic covalent cross-linking more than gel point, supermolecule Supermolecule polymer of the degree of cross linking more than its gel point is dispersed in dynamic covalent cross-linking network with graininess；
Contain a network in the dynamic aggregation object, is handed over simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network Connection, wherein the degree of cross linking of dynamic covalent cross-linking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is more than its gel point Or it is following；Supermolecule polymer of the supermolecule degree of cross linking more than its gel point is dispersed in dynamic covalent cross-linking net with graininess In network.
4. a kind of energy-absorbing method based on dynamic aggregation object according to claim 2, which is characterized in that the wherein hydrogen At least a kind of hydrogen bond group is located at the side group or side chain or side group and side chain of the dynamic aggregation object in key group.
5. a kind of energy-absorbing method based on dynamic aggregation object according to claim 2, which is characterized in that the wherein hydrogen At least a kind of hydrogen bond group contains hydrogen bond donor and hydrogen bond receptor simultaneously in key group.
6. a kind of energy-absorbing method based on dynamic aggregation object according to claim 1, which is characterized in that wherein in formula (1) X—For bromide ion；Wherein the X in formula (2) is bromine atom.
7. a kind of energy-absorbing method based on dynamic aggregation object described in any claim, feature in -6 according to claim 1 It is, wherein the dynamic aggregation object has following any character: ordinary solid, elastomer, gel, foam.
8. a kind of energy-absorbing method based on dynamic aggregation object described in any claim, feature in -6 according to claim 1 It is, constitutes the recipe ingredient of the wherein described dynamic aggregation object and further include following any or appoint and several additive or can make With object: other polymers, auxiliary agent, filler, sweller.
9. a kind of energy-absorbing method based on dynamic aggregation object according to claim 8, which is characterized in that wherein, described Other polymers are selected from following any or appoint several: natural polymer, synthetic macromolecular compound；The auxiliary agent Selected from it is following any or appoint it is several: catalyst, initiator, antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsification Agent, fire retardant, toughener, coupling agent, solvent, lubricant, release agent, plasticizer, thickener, thixotropic agent, levelling agent, coloring Agent, fluorescent whitening agent, delustering agent, antistatic agent, dehydrating agent, biocide mildewcide, foaming agent, blowing promotor, nucleating agent, rheology Agent；The filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler；Described is molten Swollen dose is selected from following any or appoints several: water, organic solvent, ionic liquid, oligomer, plasticizer.
10. a kind of energy-absorbing method based on dynamic aggregation object described in any claim in -6,9 according to claim 1, special Sign is that the energy-absorbing method is applied to defense of resistance to impact, damping, damping, buffering, explosion-proof, shellproof, sound insulation, noise elimination.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591125A (en) * 2019-07-31 2019-12-20 北京理工大学 Soluble three-dimensional crosslinked elastomer and preparation and treatment method thereof
CN114311897A (en) * 2022-01-21 2022-04-12 哈尔滨通达工业环保自动化有限公司 Vibration-damping sound-insulating material and preparation method and application thereof
US20220251308A1 (en) * 2019-07-17 2022-08-11 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220251308A1 (en) * 2019-07-17 2022-08-11 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations
US11725082B2 (en) * 2019-07-17 2023-08-15 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations
CN110591125A (en) * 2019-07-31 2019-12-20 北京理工大学 Soluble three-dimensional crosslinked elastomer and preparation and treatment method thereof
CN110591125B (en) * 2019-07-31 2021-01-26 北京理工大学 Soluble three-dimensional crosslinked elastomer and preparation and treatment method thereof
CN114311897A (en) * 2022-01-21 2022-04-12 哈尔滨通达工业环保自动化有限公司 Vibration-damping sound-insulating material and preparation method and application thereof

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