CN108342072A - A kind of dynamic aggregation object and its application with hybrid cross-linked structure - Google Patents

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

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CN108342072A
CN108342072A CN201710056050.5A CN201710056050A CN108342072A CN 108342072 A CN108342072 A CN 108342072A CN 201710056050 A CN201710056050 A CN 201710056050A CN 108342072 A CN108342072 A CN 108342072A
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dynamic
covalent
linker
network
atoms
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不公告发明人
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Weng Qiumei
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Weng Qiumei
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Priority to CN201710056050.5A priority Critical patent/CN108342072A/en
Priority to PCT/CN2018/072461 priority patent/WO2018137508A1/en
Publication of CN108342072A publication Critical patent/CN108342072A/en
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Abstract

The invention discloses a kind of dynamic aggregation objects with hybrid cross-linked structure, are the common covalent cross-linking network of carbochain or carbon heterochain containing at least one skeleton, while including dynamic covalently inorganic boric acid estersil key.Common covalent cross-linking imparts polymer with certain strength and stability.And the presence of inorganic boric acid estersil key so that polymer has good dynamic reversibility, and reflects the functional characteristics such as stimulating responsive；Also so that polymer is played good energy-absorbing effect, toughening and damping are carried out to material in specific structure.The dynamic aggregation object can be used for making damping, buffering material, defense of resistance to impact material, self-repair material, toughness material, force snesor etc..

Description

A kind of dynamic aggregation object and its application with hybrid cross-linked structure
Technical field
The present invention relates to intelligent polymer fields, and in particular to one kind is made of common covalent bond and inorganic boric acid estersil key Dynamic aggregation object with hybrid cross-linked network and its application.
Background technology
Traditional polymer is generally made of common covalent bond, and common covalent bond is due to higher bond energy, imparting Polymer is with good stability and stress bearing capacity.And dynamic covalent bond is then one kind that can carry out under certain condition can The chemical bond of back reaction, it stablizes than non-covalent bond, but bond energy is weaker than common covalent bond again, can be with by the condition in the control external world Realize the fracture and formation of dynamic covalent bond.Dynamic covalent bond is introduced into polymer, is a kind of formation novel intelligent polymer Feasible method.The meaning for introducing dynamic covalent bond in the polymer is that dynamic covalent bond is on the basis of common covalent bond, tool There is dynamic reversible characteristic possessed by noncovalent interaction in supramolecular chemistry, while it is non-covalent mutually to have evaded supermolecule again Effect bond energy itself is weaker, and stability is poor, the defect easily influenced by extraneous factor.Therefore, dynamic by introducing in the polymer State covalent bond is hopeful that the polymer with good comprehensive performance can be obtained.
Make the components such as polymer form unlimited three-dimensional net structure by crosslinked means, enables to polymer in heat The performance of stability, mechanical property, solvent resistance etc. is improved, and can be obtained with good performance and application The polymer material of value.For traditional cross-linked polymer, it is generally divided into chemical crosslinking type either physical crosslinking type.Change Crosslinking polymer is learned generally by common covalently cross-linked formation, and once being formed, then highly stable, mechanical property is also more excellent It is good；Physical crosslinking type polymer is generally cross-linked to form by noncovalent interaction, and the feature protruded is with dynamic reversible Property, the performance of cross-linked structure and polymer has changeability.And the cross-linked polymer being commonly used, often by single Common covalent bond or single dynamic covalent bond constituted, can not also well by structural with dynamic in the polymer into Row organically combines, dynamic can reverse effect and ability of regulation and control it is also extremely limited, it is therefore desirable to develop a kind of novel Polymer to solve problems of the prior art.
Invention content
The present invention is directed to above-mentioned background, provides a kind of carbochain with hybrid cross-linked structure/carbon heterochain dynamic aggregation object, Wherein include at least one common covalent cross-linking network, while wherein also including dynamic covalently inorganic boric acid estersil key.It is described Dynamic aggregation object while with certain mechanical strength and good toughness, also show excellent dynamic reversibility, And reflect the functional characteristics such as stimulating responsive, tack, energy absorption capacity, certain self-repairability.
The present invention is achieved by following technical solution：
A kind of dynamic aggregation object with hybrid cross-linked structure, wherein include at least one common covalent cross-linking network, and And at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein include that dynamic is covalently inorganic simultaneously Boric acid estersil key, wherein covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and wherein The different Si atoms being based partially in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker L, are based partially on simultaneously Different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The linker L, contains Carbon atom on dynamic covalent polymer main chain backbone；The linker Y is in dynamic covalent polymer main chain bone The structure of frame only contains (poly-) siloxane unit.
(the first network structure) in an embodiment of the invention, only there are one nets for the dynamic covalent polymer Network contains the covalently inorganic boric acid estersil key crosslinking of common covalent cross-linking and dynamic in the network, wherein common covalent cross-linking simultaneously It is carbochain or carbon heterochain structure to reach its gel point or more and its cross-linked network skeleton；Wherein, the covalent Inorganic Boron of the dynamic Any one B atom is connect with three-O- in sour estersil key, and B-O-Si dynamic of the which part based on different B atoms is covalent Different Si atoms in key are connected by linker L, while being based partially in the B-O-Si dynamic covalent bonds of different B atoms not It is connected by linker Y with Si atoms；The linker L contains the carbon on dynamic covalent polymer main chain backbone Atom, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.
(second of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；Common covalent cross-linking is contained only in 1st network, and its covalent cross-linking network skeleton is carbochain or carbon heterochain structure；2nd net Its gel point or more is reached with the dynamic crosslinking that covalently inorganic boric acid estersil key is formed in network, without more than gel point common total Valence is crosslinked, wherein covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and which part Different Si atoms in B-O-Si dynamic covalent bonds based on different B atoms are connected by linker L, while being based partially on difference Different Si atoms in the B-O-Si dynamic covalent bonds of B atoms are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer main chain backbone, the linker Y, on dynamic covalent polymer main chain backbone Structure only contain (poly-) siloxane unit.
(the third network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；The first such as described network structure of 1st network；Common covalent cross-linking is contained only in 2nd network, is free of the covalent nothing of the dynamic Machine boric acid estersil key；Wherein, at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein, institute It states any one B atom in the covalent inorganic boric acid estersil key of dynamic to connect with three-O-, and which part is based on different B atoms B-O-Si dynamic covalent bonds in different Si atoms be connected by linker L, while being based partially on the B-O-Si of different B atoms Different Si atoms in dynamic covalent bond are connected by linker Y；The linker L contains in dynamic covalently polymerization Carbon atom on owner's chain backbone, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.
(the 4th kind of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；1st network and the 2nd network are the first described network structure, and at least one common covalent cross-linking network Skeleton is carbochain or carbon heterochain structure, but described the 1st and the 2nd network are different.It is this to differ, it can lift for example, polymer Chain agent structure is different, covalent cross-linking crosslink density is different, the composition of polymer chain side group and/or side chain is different etc..
(the 5th kind of network structure) in yet another embodiment of the present invention, the dynamic covalent polymer contains at least One network, common covalent cross-linking is only contained in those networks, and at least one common covalent cross-linking network skeleton is carbochain Or carbon heterochain structure, and with dynamic, covalently inorganic boric acid estersil key cross-linked polymer is dispersed in the network in granular form In；Wherein, covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and which part base Different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker L, while being based partially on different B Different Si atoms in the B-O-Si dynamic covalent bonds of atom are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer main chain backbone, the linker Y, on dynamic covalent polymer main chain backbone Structure only contain (poly-) siloxane unit.
(the 6th kind of network structure) in yet another embodiment of the present invention, the dynamic covalent polymer only contains one A network, only contains common covalent cross-linking in the network, and the common covalent cross-linking network skeleton is carbochain or carbon heterochain structure, And the non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed in the network；Wherein, the dynamic is total Any one B atom is connect with three-O- in the inorganic boric acid estersil key of valence, and B-O- of the which part based on different B atoms Different Si atoms in Si dynamic covalent bonds are connected by linker L, while being based partially on the B-O-Si dynamics of different B atoms altogether Different Si atoms in valence link are connected by linker Y；The linker L contains in dynamic covalent polymer main chain Carbon atom on skeleton, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) silicon Oxygen alkane unit.
(the 7th kind of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network contains only common covalent cross-linking, and at least one common covalent cross-linking network bone in the 1st network and the 2nd network Frame is carbochain or carbon heterochain structure；1st network and the 2nd network can be identical or different, preferably different；At least one of which The non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed in network；Wherein, the covalent Inorganic Boron of the dynamic Any one B atom is connect with three-O- in sour estersil key, and B-O-Si dynamic of the which part based on different B atoms is altogether Different Si atoms in valence link are connected by linker L, while being based partially in the B-O-Si dynamic covalent bonds of different B atoms Different Si atoms are connected by linker Y；The linker L contains on dynamic covalent polymer main chain backbone Carbon atom, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxanes list Member.
In embodiments of the present invention, the inorganic boric acid estersil key (B-O-Si) is by inorganic compounds of boron and siliceous The silicon-containing compound of hydroxyl and/or silicone hydroxyl presoma reacts.
Wherein, the inorganic compounds of boron refers to that the boron atom in compound is not contained with carbon atom by what boron carbon key was connected Boron compound, it includes but not limited to boric acid, borate, borate, boric anhydride, halogenation boron etc. that the inorganic compounds of boron, which is selected from,.
The silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma refers to that the end group of compound and/or side group contain There are silicone hydroxyl and/or silicone hydroxyl presoma group.
In the present invention, covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms are connected by linker L, are based partially on simultaneously Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer skeleton, the linker Y only contain (poly-) siloxane unit
In embodiments of the present invention, the raw material components of dynamic aggregation object are used to prepare, the Inorganic Boron chemical combination is removed Further include the other polymers that can be added/use, auxiliary agent, filler except object and silicon-containing compound.
Wherein, the other polymers are selected from following any or appoint several：Natural polymer, synthesis tree Fat, synthetic rubber, synthetic fibers；
Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, Heat stabilizer, crosslinking agent, curing agent, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic Conditioning agent, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, Thickener, levelling agent；
Wherein, the filler is selected from following any or appoints several：Inorganic non-metallic filler, organic is filled out at metal packing Material.
In embodiments of the present invention, the form of the dynamic aggregation object or its composition includes but not limited to common solid Body, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), Foam.
In embodiments of the present invention, a kind of energy-absorbing method is provided, which is characterized in that provide a kind of with hybrid cross-linked The dynamic aggregation object of structure or its composition simultaneously progress energy-absorbing using it as energy-absorbing material, wherein the dynamic aggregation object includes At least one common covalent cross-linking network, and at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain knot Structure；Wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein the dynamic is covalently any one in inorganic boric acid estersil key A B atoms are connect with three-O-, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms It is connected by linker L, while is based partially on the different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms and passing through connection Base Y is connected；The linker L contains the carbon atom on dynamic covalent polymer skeleton；The linker Y, Structure in dynamic covalent polymer skeleton only contains (poly-) siloxane unit.
In embodiments of the present invention, the dynamic aggregation physical performance with hybrid cross-linked structure is adjustable on a large scale, It has broad application prospects, specifically, can be applied to and make damper, padded coaming, defense of resistance to impact material, fortune Dynamic protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, bulletproof glass interlayer The products such as glue, toughness material, shape-memory material, toy, force snesor.
Compared with prior art, the invention has the advantages that：
(1) common covalent cross-linking and inorganic boric acid silicon are combined in the hybrid cross-linked network structure of dynamic aggregation object of the invention Ester bond is crosslinked, and is made full use of and is combined respective advantage.Wherein, common covalent cross-linking provides one strong for dynamic aggregation object And the network structure stablized, polymer can keep balanced structure namely dimensional stability；And the covalent inorganic boric acid estersil of dynamic Key crosslinking be then dynamic aggregation object provide one covalently can spontaneously or under external influence reversible change dynamic network Structure shows collaboration in polymer network and makees to realize " being association of activity and inertia " of dynamic covalent bond and common covalent bond With.
(2) compared to traditional common covalent cross-linking polymer, the inorganic boric acid estersil bond energy in the present invention enough relies on it Higher dynamic reversibility and stress sensitivity so that cross-linked polymer can in time, promptly make a response to external force；And Compared to existing supermolecule cross-linked polymer, the inorganic boric acid estersil key in the present invention is again because its covalent property is in fracture process In can dissipate more energy, to preferably promote the energy absorption characteristics and toughness of material.And inorganic boric acid estersil key Fracture is reversible, recoverable, assigns material with durability.Based on the strong dynamic of inorganic boric acid estersil key, polymer can To show dilatancy, to generate from creep properties to elastomeric transformation, the ability of impact force dispersion is greatly improved, to Reach excellent shock resistance effect；And due to the presence of common covalent cross-linking, polymer has self-supporting, removes from using capsule The trouble that bag to polymer dress a corpse but may reveal has excellent practicability.Utilize design of the present invention It is disconnected to change traditional cross-linked polymer while remaining the characteristics such as traditional cross-linked polymer mechanical strength, stability for thinking Split that elongation is low, the defect of poor toughness, and there is excellent shock resistance, this is that the prior art is unable to reach.
(3) a kind of dynamic aggregation object with hybrid cross-linked structure of the invention, wherein including two different connections Base L and linker Y can be prepared by adjusting the ratio of the two and the structural modification of two kinds of linkers with different structure Dynamic aggregation object meet the application demand of different occasions to make dynamic aggregation object reveal abundant different performance.
(4) present invention in hybrid cross-linked dynamic aggregation object structure-rich, performance is various, and raw material sources are easy to get extensively.It is logical It crosses the functional group number adjusted in raw material compound, molecular structure, molecular weight and/or is introduced with reactivity in raw material compound Group, promote dynamic group, have functional group and/or adjustment raw material composition etc. parameters, can prepare has The dynamic aggregation object of different structure, to make dynamic aggregation object reveal abundant different performance.As one of raw material components Inorganic compounds of boron derives from a wealth of sources, property is stable and cheap, largely reduces the synthesis cost of dynamic aggregation object, Simplify preparation flow so that hybrid cross-linked dynamic aggregation object material obtained can more efficiently put into actual production and answer With extending the application field of material.
(5) dynamic response of dynamic reversible key is strong in hybrid cross-linked dynamic aggregation object, dynamic response mild condition.It compares In other existing dynamic covalent systems, the present invention take full advantage of boric acid ester bond with good thermal stability and height it is dynamic State invertibity, can without catalyst, without high temperature, illumination condition under realize dynamic aggregation object synthesis and dynamic reversibility, While improving preparation efficiency, the limitation of use environment is also reduced, extends the application range of polymer.In addition, By optionally controlling other conditions (auxiliary agent, adjustment reaction temperature is such as added), can accelerate under appropriate environment Or dynamic covalent chemical balance is quenched, it is at required state, this is in existing supramolecular chemistry and the covalent body of dynamic System the inside is more difficult to accomplish.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific implementation mode
The present invention relates to a kind of dynamic aggregation objects with hybrid cross-linked structure, wherein including at least one common covalently friendship Networking network, and at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein include dynamic simultaneously The covalent inorganic boric acid estersil key of state, wherein the dynamic covalently any one B atom and three-O- in inorganic boric acid estersil key Connection, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms are connected by linker L, The different Si atoms being based partially on simultaneously in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The company Base L is met, the carbon atom on dynamic covalent polymer main chain backbone is contained, the linker Y is covalent in dynamic Structure on main polymer chain skeleton only contains (poly-) siloxane unit.Term " polymerization " (reaction) used is chain in the present invention Propagation process/effect, including reactant have higher molecular weight by the synthesis of the reaction formations such as polycondensation, addition polymerization, ring-opening polymerisation The process of product.Among these, reactant, which is typically polymerizing power, (can spontaneously be polymerize, or can be Initiator additional can be polymerize under effect) the compounds such as monomer, oligomer, prepolymer.Gathered by a kind of reactant It closes obtained product and is known as homopolymer.The product being polymerize by two or more reactant is known as copolymer.It needs It is noted that " polymerization " in the present invention, it includes the linear growth process of reactant molecule chain, including reactant The branched process of strand, includes the annulation process of reactant molecule chain, also includes the cross-linking process of reactant molecule chain.
Term " crosslinking " (reaction) used in the present invention refers to passing through between reactant molecule and/or in reactant molecule Covalent bond is connected chemically to be formed with two dimension, three-dimensional cluster and the process for forming three-dimensional unlimited reticular pattern product in turn.It is handing over During connection, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, and it (can be two dimension or three to gradually form cluster Dimension), developing deeply is three-dimensional infinite network.Unless stated otherwise, the present invention in cross-linked structure refer in particular to gel point or more (contain, under Three-dimensional infinite network structure together), non-crosslinked includes line style, branched, cyclic annular, two-dimentional cluster and gel point three-dimensional cluster knot below Structure isogel point structure below.
Heretofore described " gel point ", expression is reactant in cross-linking process, and viscosity is uprushed, and starts to coagulate Gelatinization phenomenon reaches reflecting point when a three-dimensional infinite network, also referred to as percolation threshold for the first time.Friendship more than gel point There is co-product three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer architecture；In solidifying Glue point cross-linking products below are only loose link structure, form three-dimensional infinite network structure, are only locally lying in A small amount of three-dimensional net structure, and it is not belonging to the cross-linked network that can constitute an entirety across entire polymer architecture.
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key (is generally not more than 100 DEG C) under typical temperature and (is generally less than 1 day) more difficult be broken in the usual time comprising But it is not limited only to common carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen Key, nitrogen-nitrogen key etc..
In embodiments of the present invention, " the dynamic covalent bond ", refers to inorganic boric acid estersil key.Described is dynamic State covalent bond is also present in the side group and/or side chain and/or branch of skeletal chain in addition to being present in polymer backbone chains And/or on bifurcated chain and its on the side group and/or side chain of next stage and/or lower multistage and/or branch and/or bifurcated chain.This hair Contain boric acid estersil key in the bright side group for being also not precluded within polymer chain and/or end group.Wherein only have on cross-linked network skeleton Dynamic covalent bond could constitute dynamic covalent cross-linking.Under suitable conditions, the dynamic of any position is covalent in dynamic aggregation object Key can participate in dynamic reversible exchange.In the cross-linked network structure of dynamic aggregation object, the dynamic of dynamic covalent cross-linking is constituted Once dissociating, total effective degree of cross linking of polymeric system will reduce covalent bond.Any two it is nearest contain inorganic boric acid silicon There is no limit can for inorganic boric acid estersil bond number amount (ratio for accounting for all keys) between the common covalent cross-linking point of ester bond on skeleton To be one or more, preferably contain only there are one.When there are one containing only, dynamic aggregation object structure is more regular, and dynamic is more Add controllable.
In embodiments of the present invention, the linker L and linker Y is at least divalent, can both have and appoint It anticipates suitable topological structure, including but not limited to line style, ring-type (including but not limited to monocycle, polycyclic, nested rings, bridged ring), branch Change (including but not limited to star-like, H-type, combed, dendroid, hyperbranched), two and three dimensions cluster, and the above structure is arbitrary Appropriate combination, the even particle (including fiber and sheet-like particle) with common covalent cross-linking；The two also may each be homopolymerization Object can also be copolymer.Wherein, the linker L can be low molecular weight or high molecular weight skeleton on contain carbon atom Linker, preferably molecular weight is more than the macromolecule linker of 1000Da, the amount of carbon atom contained on its more preferable skeleton Molecular weight not less than 20 is more than the macromolecule linker of 1000Da.Also contain optional hetero atom on the linker L skeletons It and/or can be with the Elements Atom of formation element organic group, wherein the hetero atom optionally contained can be any appropriate miscellaneous original Son, including but not limited to O, N, S；The Elements Atom optionally contained can be any appropriate Elements Atom, including but unlimited In P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir.It is preferred that linker L by carbon atom directly with the Si atom phases of B-O-Si keys Connection, can not only obtain the dynamic of B-O-Si keys, but also can maximally utilise the performance of carbon atoms linker L.Institute The linker L for stating carbon atoms can have any one or more glass transition temperatures, be higher than the glass transition temperature of room temperature Degree can assign the better rigidity of dynamic covalent polymer and modulus, and the glass transition temperature less than room temperature can assign dynamic copolymerization The better flexibility of object, extensibility and plasticity.The linker L of the carbon atoms is preferably alkyl, polyolefin-based, polyethers Base, polyester base, polyurethane, polyureas base, polysulfide for amine ester group, polyacrylic acid ester group, polyacrylamide base, makrolon base, Polyethers sulfuryl, polyarylsulfone (PAS) base, polyether-ether-ketone base, polyimide-based, polyamide-based, polyamine group, polyphenyl ether, polyphenylene sulfide ether, Polyphenyl sulfuryl, but the present invention is not limited only to this.The linker Y be (poly-) siloxanes, can also have any one or Multiple glass transition temperatures, but typically each it is less than room temperature.According to the embodiment of the present invention, in a dynamic covalent polymer Different linker L and linker Y can be contained；Can also there are other linkers, this hair in addition to linker L and linker Y It is bright not to be limited, but preferably only linker L and linker Y.Exist while linker L and linker Y and assigns the mechanics of materials The adjustability that performance, dynamic etc. are had excellent performance is suitble to obtain strong dynamic because linker Y has lower glass transition temperatures Property and pliability etc.；And linker L is more suitable for obtaining good mechanical property.
Can include one or more kinds of polymer, but common including at least one in the dynamic aggregation object of the present invention The network of covalent cross-linking namely at least one network are to be crosslinked with common covalent bond and reach gel point or more.Institute Stating dynamic, covalently inorganic boric acid estersil key can constitute crosslinking together in common covalently cross-linked network, can also independent shape It, can also be in non-crosslinked chain at dynamic covalent cross-linking network.Because including at least the network of a common covalent cross-linking, Even if in the case where all dynamic keys will be completely dissociated, polymeric system of the invention can also keep balanced structure, namely Basic shape can be kept not occur completely melting and dissolving.Keeping balanced structure to mean can be with self-supporting, to poly- The many uses for closing object are most important, such as sealing ring, tire etc..
In the present invention, " skeleton " refers to structure on the chain length direction of polymer chain.It is described for cross-linked polymer " main chain ", refer to the arbitrary segment being present on cross-linked network skeleton comprising the main chain on unlimited three-dimensional network skeleton It is linked with crosslinking；Wherein, the crosslinking link between polymer chain can be an atom, a singly-bound, a group, a chain Section, a cluster etc..For the polymer of non-crosslinking structure, " main chain " refers to chain link most if not otherwise indicated More chains；Wherein, " side chain " refers to that same main polymer chain skeleton is connected and is distributed in the link of skeleton side Structure；Wherein, it can also be the chain structure that other come out from arbitrary chain bifurcated that " branch "/" bifurcated chain ", which can be side chain,. Wherein, " side group " refers to that the arbitrary chain of same polymer is connected and is distributed in the chemical group of chain side.For " side Chain ", " branch " and " side group " can have multilevel hierarchy namely side chain/branch that can continue to carry side group and side chain/branch, Side chain/branch of side chain/branch can continue have side group and side chain/branch.Wherein, " end group " is referred to arbitrary Chain is connected and is located at the chemical group of chain end.For hyperbranched and dendroid chain and its relevant branched chain structure, branch Main chain can also be considered as, but the branch of usually outermost is considered merely as branch.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention Can include to be selected from the option of the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
In embodiments of the present invention, the inorganic boric acid estersil key (B-O-Si) is by inorganic compounds of boron and siliceous The silicon-containing compound of hydroxyl and/or silicone hydroxyl presoma reacts.
The inorganic compounds of boron refers to that the boron atom in compound does not contain boronation with carbon atom by what boron carbon key was connected Close object.
The inorganic compounds of boron is selected from (including but not limited to) boric acid, borate, borate, boric anhydride, halogenation boron.Boron Acid can be ortho-boric acid, metaboric acid, tetraboric acid.Borate includes the alkyl and allyl ylboronic acid for being hydrolyzed into boric acid in the presence of water The organic group borate of ester/tri-, such as trimethylborate, triethyl borate, triphenyl borate, three benzyl ester of boric acid, three hexamethylene of boric acid Ester, boric acid three (methyl silicane ester), three tert-butyl ester of boric acid, three-n-pentyl borates, three sec-butyl borates, DL- menthyls Borate, three (4- chlorphenyls) borates, 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids ester, three (2- methoxyl group second Base) borate, benzyl dihydro borate, diphenyl hydrogen borate ester, isopropanol pinacol borate, triethanolamine borate etc.. Suitable boric anhydride is B except including general formula2O3Outside typical boron oxide, further include but be not limited only to tri-alkoxy boroxin and Its derivative, for example, trimethoxy boroxin, three isopropoxy boroxins, 2,2 '-oxygen it is bis- [4,4,6- trimethyls -1,3, 2- dioxa boroxanes etc..Suitable borate includes but are not limited to five boric acid diammoniums, sodium borate decahydrate (borax), five Potassium borate, hypoboric acid magnesium, single line borate, three barium borates, zinc metaborate, tripotassium borate, ortho-boric acid molysite.Suitable halogenation boron Include but are not limited to boron trifluoride, boron chloride, Boron tribromide, triiodide boron, four chlorinations, two boron etc..Suitable inorganic boronation Close the partial hydrolysate that object further comprises aforementioned borate.Typically, it is B that inorganic compounds of boron, which is general formula,2O3[CAS is registered Number #1303-86-2] boron oxide or general formula be H3BO3The boric acid of [CAS registration numbers #10043-35-3].As an example, suitably The chemical structural formula of inorganic compounds of boron is as follows, however, the present invention is not limited thereto：
The silicon-containing compound containing silicone hydroxyl and/or silicone hydroxyl presoma refers to that the end group of compound and/or side group contain There are silicone hydroxyl and/or silicone hydroxyl presoma group.In the present invention, described siliceous containing silicone hydroxyl and/or silicone hydroxyl presoma Compound itself can contain connection L and/or linker Y, or can pass through and generate linker L after suitably chemically reacting And/or linker Y.Especially can be to contain since linker L contains the carbon atom on dynamic covalent polymer main chain backbone Carbon polymer linker can obtain the various dynamic aggregation owner's chain backbone of structure-rich, performance, especially main chain backbone carbon Presence can facilitate and obtain higher dynamic aggregation object mechanical property, impressionability.
It is above-mentioned containing linker Y or can by suitably chemically react generate containing linker Y containing silicone hydroxyl and/or The silicon-containing compound of silicone hydroxyl presoma is (poly-) silicone compounds, refers to that silicone hydroxyl and/or silicon are contained in the end of compound Hydroxyl groups precursors end group, and the main chain and/or side chain that are connected with the end group and/or other chain structures are any appropriate (poly-) Siloxane structure and can make the inorganic boric acid estersil key (B-O-Si) to be formed contain the linker Y compound. The main chain of (poly-) siloxanes or agent structure etc. are by-(SiR1R2-O)nUnit forms, wherein n is siloxane unit (SiR1R2- O) quantity for the integer more than or equal to 1 can be fixed value or average value；R1、R2To be connected to silicon atom On group/segment, be each independently selected from H, halogen atom and any other suitable organic and inorganic group/segment, including Hydroxyl and other reactive organic groups；Preferably organic group/segment, more preferably carbon containing organic group/segment.Institute It is poly- selected from small molecule silicone compounds and macromolecular to state (poly-) silicone compounds containing silicone hydroxyl and/or silicone hydroxyl presoma Silicone compounds can be organic or inorganic compound, including silica.(poly-) silicone compounds can have Any appropriate topological structure, including but not limited to line style, ring-type (include but not limited to monocycle, polycyclic, bridged ring, nested rings), The form of branched (including but not limited to combed, H-type, star-like, dendritic, hyperbranched type), two-dimensional/three-dimensional cluster, and combinations thereof.
Heretofore described silicone hydroxyl refers to a hydroxyl institute group being connected by silicon atom and with the silicon atom At structural motif (Si-OH), wherein silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with a carbon Atom is connected by silicon-carbon bonds, and at least one organic group is keyed to by the silicon-carbon on silicon atom) or nothing Machine silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, silicon A hydroxyl (- OH) in hydroxyl is a functional group.One (poly-) siloxanes can contain multiple silicone hydroxyls, and multiple Si are former Son can contain hydroxyl, can also contain multiple hydroxyls on the same Si atoms.
Heretofore described silicone hydroxyl presoma, refer to one be connected by silicon atom and with the silicon atom can Hydrolysis obtains the structural motif (Si-Z) that the group of hydroxyl is formed, wherein Z is that hydrolyzable obtains the group of hydroxyl, optional From halogen, cyano, oxygen cyano, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketone Oximido, alkoxide group etc..Suitable silicone hydroxyl presoma citing is such as：Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3, Si- OB(OCH3)2, Si-NH2, Si-N (CH3)2, Si-OCH3, Si-COCH3, Si-OCOCH3, Si-CONH2, Si-O-N=C (CH3)2, Si-ONa.In the present invention, the group (Si-Z) that a hydrolyzable in silicone hydroxyl presoma obtains silicone hydroxyl is an official It can group.One (poly-) siloxanes can contain multiple silicone hydroxyl presomas, and multiple Si atoms can contain Z group, the same Si Multiple Z groups can also be contained on atom.
In order to illustrate the heretofore described linker L containing carbon atoms silicon-containing compound and its produce described contain The silicon-containing compound of linker L can be exemplified below, but the present invention is not limited only to this,
Wherein m, n, the quantity that x, y, z is repetitive unit, can be fixed value or average value.
For polysiloxanes, silicone hydroxyl can be in the end of polymer chain, can also be in the side group of polymer chain；Equally Ground, for the organopolysiloxane of siliceous hydroxyl groups precursors, silicone hydroxyl presoma can be in the end of polymer chain, can also be The side group of polymer chain.For small molecule siloxanes, silicone hydroxyl/silicone hydroxyl body equally can be in end group or side group.
In the present invention, described (poly-) silicone compounds containing silicone hydroxyl and/or silicone hydroxyl presoma can illustrate such as Under, the present invention is not limited only to this：
Wherein m, n, the quantity that x, y, z is repetitive unit, can be fixed value or average value.
In the present invention, any appropriate inorganic compounds of boron may be used and contain silicone hydroxyl and/or silicone hydroxyl presoma Compound combination generate Inorganic Boron acid estersil key, it is preferred to use inorganic boric acid and the macromolecular compound containing silicone hydroxyl, nothing Machine boric acid and macromolecular compound, the inorganic borate (salt) of siliceous hydroxyl groups precursors come with the macromolecular compound containing silicone hydroxyl Form inorganic boric acid estersil key, more preferably using inorganic boric acid with containing silicone hydroxyl macromolecular compound, inorganic borate with contain The macromolecular compound of silicone hydroxyl forms inorganic boric acid estersil key, more preferably using inorganic borate and big point containing silicone hydroxyl Sub- compound forms inorganic boric acid estersil key.
In embodiments of the present invention, the dynamic aggregation can be obtained by generating inorganic boric acid estersil key Object, can also first prepare the compound containing the inorganic boric acid estersil key again polymerized/cross-linked to generate the dynamic aggregation Object.In the present invention, the polyvalency based on Si atoms, a Si atom for participating in forming B-O-Si on the silicon-containing compound Three B-O-Si keys can be at most formed, a Si atom is shared；And since boron atom is trivalent structure, polymerization process life It can be easy to cause to form bifurcated and can be crosslinked in turn at the inorganic boric acid estersil key.
In the present invention, dynamic covalent polymer itself can have any appropriate topological structure, including but not limited to Line style, ring-type (include but not limited to monocycle, polycyclic, nested rings, bridged ring), it is branched (including but not limited to starlike, H-type, pectination, It is dendroid, hyperbranched), two-dimensional/three-dimensional cluster, three-dimensional infinite network cross-linked structure and combinations of the above form.Polymer chain With side group, side chain, branch, and side group, side chain, branch can continue, with side group, side chain, branch, can also have Multilevel hierarchy.
(the first network structure) in an embodiment of the invention, only there are one nets for the dynamic covalent polymer Network contains the covalently inorganic boric acid estersil key crosslinking of common covalent cross-linking and dynamic in the network, wherein common covalent cross-linking simultaneously It is carbochain or carbon heterochain structure to reach its gel point or more and its cross-linked network skeleton；Wherein, the covalent Inorganic Boron of the dynamic Any one B atom is connect with three-O- in sour estersil key, and B-O-Si dynamic of the which part based on different B atoms is covalent Different Si atoms in key are connected by linker L, while being based partially in the B-O-Si dynamic covalent bonds of different B atoms not It is connected by linker Y with Si atoms；The linker L contains the carbon on dynamic covalent polymer main chain backbone Atom, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit. In the network structure, it can keep balanced structure, inorganic boric acid estersil key that can provide additional move by common covalent cross-linking State covalent cross-linking and dynamic covalency, the dynamic covalent polymer obtained not only have self-supporting energy, also have significant Dilatancy and generate elastic enhancing, performance simple in structure is excellent.
(second of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；Common covalent cross-linking is contained only in 1st network, and its covalent cross-linking network skeleton is carbochain or carbon heterochain structure；2nd net Its gel point or more is reached with the dynamic crosslinking that covalently inorganic boric acid estersil key is formed in network, without more than gel point common total Valence is crosslinked, wherein covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and which part Different Si atoms in B-O-Si dynamic covalent bonds based on different B atoms are connected by linker L, while being based partially on difference Different Si atoms in the B-O-Si dynamic covalent bonds of B atoms are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer main chain backbone, the linker Y, on dynamic covalent polymer main chain backbone Structure only contain (poly-) siloxane unit.In the network structure, balance knot is kept by the common covalent cross-linking in the 1st network Structure, the inorganic boric acid estersil key in the 2nd network provide dynamic covalency, and two networks are orthogonal each other, and can be on preparing Minimally it is limited to interfering with each other for raw material composition.
(the third network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；The first such as described network structure of 1st network；Common covalent cross-linking is contained only in 2nd network, is free of the covalent nothing of the dynamic Machine boric acid estersil key；Wherein, at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein, institute It states any one B atom in the covalent inorganic boric acid estersil key of dynamic to connect with three-O-, and which part is based on different B atoms B-O-Si dynamic covalent bonds in different Si atoms be connected by linker L, while being based partially on the B-O-Si of different B atoms Different Si atoms in dynamic covalent bond are connected by linker Y；The linker L contains in dynamic covalently polymerization Carbon atom on owner's chain backbone, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.In the network structure, balanced structure is kept by the common covalent cross-linking in the 1st network and the 2nd network, Inorganic boric acid estersil key in 1st network provides dynamic covalency, and the dual network structure that two common covalent cross-linkings provide is in power Learning in performance has advantage outstanding, adds additional dynamic covalent cross-linking, can be elevated in mechanical property.
(the 4th kind of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network；1st network and the 2nd network are the first described network structure, and at least one common covalent cross-linking network Skeleton is carbochain or carbon heterochain structure, but described the 1st and the 2nd network are different.It is this to differ, it can lift for example, polymer Chain agent structure is different, covalent cross-linking crosslink density is different, the composition of polymer chain side group and/or side chain is different etc..The reality It applies in mode, by adjusting the structure of the 1st network and/or the 2nd network, the mesh for accurately controlling dynamic aggregation physical performance can be reached 's.
(the 5th kind of network structure) in yet another embodiment of the present invention, the dynamic covalent polymer contains at least One network, common covalent cross-linking is only contained in those networks, and at least one common covalent cross-linking network skeleton is carbochain Or carbon heterochain structure, and with dynamic, covalently inorganic boric acid estersil key cross-linked polymer is dispersed in the network in granular form In；Wherein, covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and which part base Different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker L, while being based partially on different B Different Si atoms in the B-O-Si dynamic covalent bonds of atom are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer main chain backbone, the linker Y, on dynamic covalent polymer main chain backbone Structure only contain (poly-) siloxane unit.In the embodiment, common covalent cross-linking provides balanced structure, with inorganic boric acid silicon The crosslinked dynamic aggregation object of ester bond is dispersed in granular form in common covalent cross-linking network, and it is swollen that when stress can provide part Material hardness caused by fluidity and intensity increase, and achieve the purpose that organic regulation and control power dissipation.
(the 6th kind of network structure) in yet another embodiment of the present invention, the dynamic covalent polymer only contains one A network, only contains common covalent cross-linking in the network, and the common covalent cross-linking network skeleton is carbochain or carbon heterochain structure, And the non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed in the network；Wherein, the dynamic is total Any one B atom is connect with three-O- in the inorganic boric acid estersil key of valence, and B-O- of the which part based on different B atoms Different Si atoms in Si dynamic covalent bonds are connected by linker L, while being based partially on the B-O-Si dynamics of different B atoms altogether Different Si atoms in valence link are connected by linker Y；The linker L contains in dynamic covalent polymer main chain Carbon atom on skeleton, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) silicon Oxygen alkane unit.In the embodiment, common covalent cross-linking provides balanced structure, the dilatancy of noncrosslinking dynamic covalent polymer Complete viscous loss can be provided in stress, play strong energy-absorbing function.
(the 7th kind of network structure) in yet another embodiment of the present invention, there are two the dynamic covalent polymer contains Network contains only common covalent cross-linking, and at least one common covalent cross-linking network bone in the 1st network and the 2nd network Frame is carbochain or carbon heterochain structure；1st network and the 2nd network can be identical or different, preferably different；At least one of which The non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed in network；Wherein, the covalent Inorganic Boron of the dynamic Any one B atom is connect with three-O- in sour estersil key, and B-O-Si dynamic of the which part based on different B atoms is altogether Different Si atoms in valence link are connected by linker L, while being based partially in the B-O-Si dynamic covalent bonds of different B atoms Different Si atoms are connected by linker Y；The linker L contains on dynamic covalent polymer main chain backbone Carbon atom, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxanes list Member.In the present embodiment, two common covalent cross-linking networks provide balanced structure and excellent mechanics as dual network structure Performance, and the dilatancy for disperseing non-crosslinked dynamic aggregation object therein can provide complete viscous loss in stress, play Strong energy-absorbing function.
In addition to the embodiment of above-mentioned seven kinds of hybrid cross-linked network structures, the present invention can also have other diversified miscellaneous Change cross-linked network structure embodiment, can include three or its above identical or different network in an embodiment, Can include that different common covalent cross-linkings and/or the inorganic boric acid estersil key of different dynamics are crosslinked in the same network, it is each Chemical constitution, topological structure, degree of cross linking of network etc. can be identical or different, can disperse/fill crosslinking in network structure And/or non-cross-linked polymer ingredient, skeleton hydrogen bond group can also be contained in each ingredient.Inorganic boric acid estersil key is for providing altogether Valence dynamic property, including but not limited to plasticity and self-repairability can utilize its good dynamic property, assign polymer and answer The performances such as power/strain-responsive, ultra-tough, selfreparing, shape memory.Those skilled in the art according to the present invention can patrol Volume and train of thought, rationally and effectively realize.
In embodiments of the present invention, a kind of energy-absorbing method is provided, which is characterized in that provide a kind of with hybrid cross-linked The dynamic aggregation object of structure or its composition simultaneously progress energy-absorbing using it as energy-absorbing material, wherein the dynamic aggregation object includes At least one common covalent cross-linking network, and at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain knot Structure；Wherein include dynamic covalently inorganic boric acid estersil key simultaneously, wherein the dynamic is covalently any one in inorganic boric acid estersil key A B atoms are connect with three-O-, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms It is connected by linker L, while is based partially on the different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms and passing through connection Base Y is connected；The linker L contains the carbon atom on dynamic covalent polymer skeleton；The linker Y, Structure in dynamic covalent polymer skeleton only contains (poly-) siloxane unit.
In embodiments of the present invention, the hydrogen bond group on main polymer chain skeleton, as " skeleton hydrogen bond group " are Refer at least partly atom in the group directly to participate in building the polymer on continuous main polymer chain or cross-linked network skeleton Main chain or crosslinking link.The skeleton hydrogen bond group can be generated in polymer polymerizing/cross-linking process, namely pass through and to be formed The hydrogen bond group and generate polymerized/cross-linked；Can also be to be generated in advance to carry out polymerized/cross-linked again.
In embodiments of the present invention, the skeleton hydrogen bond group can be selected from for example, amide groups, carbamate Base, thiocarbamate base, silicon are for carbamate groups, urea groups and derivative based on the above group.It is preferred that amino first Perester radical, urea groups and their derivative.As an example, it can enumerate such as lower structure, but the present invention is not limited only to this：
In the present invention, it can contain in same polymer and have more than a kind of above-mentioned skeleton hydrogen bond group, the same net It can also contain in network and have more than a kind of above-mentioned skeleton hydrogen bond group.To the compound of the skeleton hydrogen bond group can be imported simultaneously It is not particularly limited, is correspondingly formed reaction type and mode of the group etc. and is also not particularly limited.
In embodiments of the present invention, the form of the dynamic aggregation object composition with hybrid cross-linked structure can be Ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid Body swell gel), foam etc..Wherein, the shape and volume of dynamic aggregation object ordinary solid are relatively more fixed, and intensity is high, and density is big, Anti-explosion wall or apparatus housings suitable for high intensity；Elastomer has the general properties of ordinary solid, but more soft has Elasticity.Dynamic aggregation object gel soft texture, there is preferable energy absorption capacity and elasticity, is suitable for preparing the energy-absorbing material of high-damping； Dynamic aggregation object foamed material is when having the advantages that the general foamed plastics such as density is low, light, specific strength is high, soft foam material Also there is good elasticity and energy absorption capacity.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.
In the preparation process of dynamic aggregation object expanded material, mainly using mechanical foaming method, physical blowing method, chemistry hair Three kinds of methods of bubble method foam to dynamic aggregation object.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be gelled, cures and become foamed material.For shorten molding cycle can be passed through air and be added emulsifier or Surfactant.
Wherein, the physical blowing method, be realized using physical principle in the preparation process of dynamic aggregation object it is poly- The foaming for closing object, generally comprises following five kinds of methods：(1) inert gas blown method, i.e., inert gas under pressurized condition It is pressed into molten polymer or pasty material, then decompression heating, makes the gas expansion of dissolving and foam；(2) low boiling point is utilized Liquid evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, keep liquid molten Enter in polymer beads, then heat and soften polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching uses liquid Body medium, which immerses in polymer, dissolves the solid matter added in advance, makes to occur a large amount of holes in polymer and be in foaming Shape, such as by solable matter salt, starch elder generation and mixed with polymers, put in water after being shaped to product, then by product It handles repeatedly, solable matter is dissolved out to get to open-celled foam product；(4) hollow microsphere method is added in the polymer Become obturator-type foam through solidification after hollow microsphere；(5) freeze-drying is initially formed gel or swelling body, then carries out Freeze-drying obtains foam.Wherein, it is sent out preferably by the method for dissolving in inert gas and low-boiling point liquid in the polymer Bubble.Using physical blowing method, has and operate the advantages that Poisoning is smaller, and foaming raw material cost is relatively low, foaming agent noresidue body.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally comprise following two methods：(1) thermal decomposable foaming agent foaming utilizes chemical foaming agent The gas decomposed to give off after heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, that is, utilize hair The chemical reaction occurred between two or more components in foam system, generating inert gas (such as carbon dioxide or nitrogen) causes Polymer is expanded and is foamed.Polymerisation and foamable reaction balance carry out in order to control in foaming process, to ensure that product has preferably Quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by adding in the polymer The method of chemical foaming agent is added to foam.
In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to be molded dynamic aggregation object foamed material.
Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material is direct plungeed into die cavity to carry out foaming；Two-step method refers to first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam is molded ratio Two-step method is easy to operate and production efficiency is high, therefore it is preferred that one-step method carries out moulded from foam molding.
Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve In certain flow rate injecting material melt, then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent Under the action of form nuclei of bubbles.After expansion stage and solidifying and setting stage are all happened at full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while making foam solidifying and setting with the cooling of mold.
Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.Since it can not only realize continuous production, and it is more more competitive than injection-expansion molded in cost, because This is current most widely used foaming technology.
In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is half open-celled structure that leading to again, which has mutual disconnected structure then,.It, also can be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes：(1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be more than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are more than 0.4g/cm3, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm3, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm3, expansion ratio is more than 9.
It is used to prepare the composition of raw materials component of dynamic aggregation object, except the inorganic compounds of boron and (poly-) silicone compound Further include the other polymers that can be added/use, auxiliary agent, filler except object, these can add/and it can be to be blended, join using object With the form and inorganic compounds of boron of chemical reaction and the reaction product of silicon-containing compound collectively as with hybrid cross-linked structure Dynamic aggregation composition formula component, or play the role of in the preparation process of dynamic aggregation object improving processing performance.
The addible other polymers can play in system as additive and improve material property, assign Material new capability is given, materials'use and economic benefit is improved, has the function that material comprehensively utilizes.Other addible polymerizations Object can be selected from natural polymer, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to the polymer that is added Character and possessed molecular weight do not limit, can be oligomer or high polymer, root according to the difference of molecular weight Can be homopolymer or copolymer according to the difference of polymeric species, it in the specific use process should be according to the performance of target material And actual fabrication process needs and selected.
When addible other polymers are selected from natural polymer, it can be selected from following any or appoint several Natural polymer：Natural rubber, chitosan, chitin, native protein etc..
When addible other polymers are selected from synthetic resin, it can be selected from following any or appoint several synthesis trees Fat：Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), in it is close Spend polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, poly- third Acrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- carbonic acid Ester, dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, the copolymerization of tetrafluoroethylene-perfluoro propane Object, polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact Polystyrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetate second Enoate copolymer, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-second Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP) etc..
When addible other polymers are selected from synthetic rubber, it can be selected from following any or appoint several synthesis rubbers Glue：Isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorine rubber Glue, lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc..
When addible other polymers are selected from synthetic fibers, it can be selected from following any or appoint several synthesis fine Dimension：Viscose fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane fiber, gathers at copper ammonia fiber Dralon, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..
In the preparation process of polymer material, the preferred natural rubber of addible other polymers, polyethylene, poly- third Alkene, vinyl-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, epoxy Resin, phenolic resin, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, Silicon rubber, polyurethane rubber, thermoplastic elastomer (TPE).
The auxiliary agent for adding/using, can improve material preparation process, improve product quality and yield, drop Low product cost assigns product certain distinctive application performance.The addible auxiliary agent is selected from following any or appoints Several auxiliary agents：Additive synthesis, including catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer； Improve the auxiliary agent of mechanical property, including crosslinking agent, curing agent, chain extender, toughener, coupling agent；The auxiliary agent of processing performance is improved, Including lubricant, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change surface The auxiliary agent of performance, including antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, disappears Photo etching；Fire retardantization and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent.
Catalyst in the auxiliary agent for adding/using can reduce reaction activation by changing reaction path It can accelerate the reaction rate of reactant during the reaction.In embodiments of the present invention, the catalyst include but It is not limited only to：(1) polyurethane catalyst for synthesizing：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylamino second Base) ether, 2- (2- Dimethylamino-ethoxies) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanols of N- Amine, N- (dimethylamino-propyl) diisopropanolamine (DIPA), N, N, N '-trimethyl-N '-ethoxy diamine ethylether, two Asia third of tetramethyl Base triamine, N, N- dimethyl cyclohexyl amines, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', the sub- second of N ', N '-pentamethyl two Base triamine, N, N- dimethylethanolamines, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls Caproic acid, N, N- dimethyl benzylamines, N, N- dimethyl cetylamines etc.；Organometallic catalysts, such as stannous octoate, dibutyl tin two Laurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, levulinic Ketone iron, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc..(2) polyolefin synthesis is used Catalyst：Such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, a chlorine diethyl Aluminium, titanium tetrachloride, titanium trichloride, 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 reactions share concerted catalysis by monovalence copper compound and amine ligand.Monovalence copper compound can be selected from Cu (I) salt, such 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；It can also be by elemental copper and cupric compound (such as CuSO4、Cu(OAc)2) former during the reaction Position generates；Wherein, the preferred CuBr and CuI of Cu (I) salt, the preferred CuBr (PPh of Cu (I) complex compound3)3.Amine ligand can be selected from three [(1- Benzyl -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), three [(1- tertiary butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；Wherein, the preferred TBTA of amine ligand And TTTA.(4) thiol-ene catalysts：Photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyls phenylacetone, 2,2- dimethoxy -2- phenyl acetophenones etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- bis- Dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01- 2wt%.
Initiator in the auxiliary agent for adding/using, can cause monomer molecule in polymerization process It activates and generates free radical, improve reaction rate, reaction is promoted to carry out, include but are not limited to following any or appoint several draw Send out agent：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, peroxide Change bis- (4- tert-butylcyclohexyls) esters of two dicyclohexyl carbonates, dicetyl peroxydicarbonate, tert butyl peroxy benzoate, tertiary butyl Peroxidating pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred peroxidating of initiator Lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1-1wt%.
Antioxidant in the auxiliary agent for adding/using can delay the oxidation process of polymer samples, ensure Material can be carried out successfully preparing processing and extend its service life, included but are not limited to following any or appointed several anti- Oxygen agent：Hinered phenols, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyls Base phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl- 6- tert-butyl phenols]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros are equal Triazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent for adding/using can prevent polymer samples from light aging occurs, and extend Its service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide Titanium, zinc oxide, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxies two Benzophenone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzo three Azoles, 2,4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethyls Own ester；Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as Bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl esters), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light Stabilizer, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2, 2,6,6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- bis- uncles Butyl benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, N '-di-n-butyl dithiocarbamates Nickel formate etc.；Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent for adding/using enables to polymer samples processing or using Chemical change does not occur because heated in journey, or delays these variations to achieve the purpose that prolong the service life comprising but It is not limited only to following any or appoints several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, disalt Base lead stearate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, two Alkali lead phthalate, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, hard Resin acid calcium, lead stearate, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, tin dilaurate di-n-octyl Tin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital Tin C-102, dimercapto acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptans type Salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxyfatty acid Ester, epoxy resin；Phosphorous acid esters, as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, Aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Wherein, The preferred barium stearate of heat stabilizer, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat used Stabilizing agent dosage is not particularly limited, generally 0.1-0.5wt%.
Crosslinking agent in the addible auxiliary agent, cooperation need to carry out crosslinked reactant in dynamic aggregation object Component is used, and can play bridging action between the polymer molecule of line style, so that multiple linear molecules is mutually bonded and is cross-linked into Reticular structure can further increase the crosslink density and cross-link intensity of polymer, improve heat resistance and the use of polymer Service life, while improving the mechanical performance and weatherability of material comprising but be not limited only to following any or appoint several crosslinking agents： Polypropylene glycol glycidol ether, zinc oxide, aluminium chloride, aluminum sulfate, chromic nitrate, ethyl orthosilicate, methyl orthosilicate, to toluene sulphur Acid, paratoluensulfonyl chloride, diacrylate -1,4- butanediol esters, ethylene glycol dimethacrylate, butyl acrylate, isopropanol Aluminium, zinc acetate, titanium acetylacetone, aziridine, isocyanates, phenolic resin, hexamethylenetetramine, cumyl peroxide, mistake Aoxidize lauroyl, peroxidating stearoylketene, benzoyl peroxide, cyclohexanone peroxide, benzoyl peroxide ethyl ketone, two tertiary fourth of peroxidating Base, adjacent benzene peroxide dicarboxylate, isopropyl benzene hydroperoxide, three tert-butyl peroxy base silane of vinyl, the tertiary fourth of diphenyl-two Peroxide base silane, trimethyl t-butyl peroxy silane etc..Wherein, the preferred cumyl peroxide of crosslinking agent (DCP), benzoyl peroxide Formyl (BPO), peroxidating 2,4 dichloro benzene formyl (DCBP).Dosage of crosslinking agent used is not particularly limited, generally 0.1- 5wt%.
Curing agent in the addible auxiliary agent, cooperation need to carry out cured reactant in dynamic aggregation object Component is used, and the curing reaction of reactant composition in the course of the polymerization process can be promoted or control comprising but be not limited only to Any below or several curing agent：Amine curing agent, such as ethylenediamine, diethylenetriamine, triethylene tetramine, dimethylamino third Amine, hexamethylenetetramine, m-phenylene diamine (MPD)；Acid anhydride type curing agent, such as phthalic anhydride, maleic anhydride, pyromellitic acid two Acid anhydride；Amides curing agent, such as Versamid；Imidazoles, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl miaows Azoles；Boron trifluoride complex etc..Wherein, the preferred ethylenediamine of curing agent (EDA), diethylenetriamine (DETA), phthalic anhydride, Maleic anhydride, hardener dose used are not particularly limited, generally 0.5-1wt%.
Chain extender in the auxiliary agent for adding/using, can be with the reaction-ity group reaction on reactant molecule chain And make strand extension, molecular weight increase, be commonly used for preparing addible polyurethane/polyurea comprising but be not limited only to Under it is any or appoint several chain extenders：Polyalcohols chain extender, such as ethylene glycol, propylene glycol, diglycol, glycerine, three hydroxyls Methylpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, hydroquinone two hydroxy ethyl ether (HQEE), the double hydroxyls of resorcinol Ethylether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, as diaminotoluene, diamino dimethylbenzene, tetramethyl are sub- Xylylene diamine, tetraethyl diphenyl methylene diamines, tetra isopropyl hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminos Methyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiands (MOCA), 3,5- dimethyl sulphur-based first Phenylenediamine (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1,3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcohol Amine chain extender, such as triethanolamine, triisopropanolamine, N, bis- (2- hydroxypropyls) aniline of N '-.Chain extender dosage used is without spy It does not limit, generally 1-20wt%.
Toughener in the auxiliary agent for adding/using can reduce polymer samples brittleness, increase toughness, carry High material bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-fourth two Alkene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, propylene Nitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, benzene Ethylene-butadiene-styrene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene (ABS) copolymerization Object (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), methyl methacrylate-butadiene-styrene copolymerization Resin (MBS), chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent for adding/using, can improve polymer samples and inorganic filler or increasing The interface performance of strong material, reduces the viscosity of material melt in plastic processes, improves the dispersion degree of filler and is added with improving Work performance, and then product is made to obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any Kind appoints several coupling agents：Chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, Aluminate Coupling agent etc.；Wherein, the preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(2,3- epoxies third Oxygen) propyl trimethoxy silicane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5- 2wt%.
Lubricant in the auxiliary agent for adding/using can improve the lubricity of polymer samples, reduce and rub It wipes, reduce Interface Adhesion performance comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbons Class, such as solid paraffin, microcrystalline wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, it is such as stearic Acid, hydroxy stearic acid；Fatty acid ester, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax； Aliphatic amide type, such as stearmide or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylenes are double stearic Amide；Fatty alcohol and polyalcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, Barium stearate, magnesium stearate, zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight Polyethylene.Lubricant quantity used is not particularly limited, generally 0.5-1wt%.
Releasing agent in the auxiliary agent for adding/using, it can make polymer samples be easy to demould, surface is smooth, It is clean comprising but be not limited only to following any or appoint several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon Oil, methyl phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon Rubber etc.；Wherein, the preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5-2wt%.
Plasticizer in the auxiliary agent for adding/using, can increase the plasticity of polymer samples so that polymerization Hardness, modulus, softening temperature and the brittle temperature of object decline, and elongation, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fat Fat esters of gallic acid, such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite Esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyls) oneself Ester, epoxy soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box acetylated castor oil Sour methyl esters；Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester, phenyl alkylsulfonate, Trimellitate, citrate and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), adjacent benzene Dibutyl carboxylic acid (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), O-phthalic Sour diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Foaming agent in the auxiliary agent for adding/using can make polymer samples foaming pore-forming, to obtain matter Gently, heat-insulated, sound insulation, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.
Dynamic regulation agent in the auxiliary agent for adding/using can be promoted and adjust dynamic aggregation object dynamic, with Just the expected performance of optimization is obtained, is usually that either free carboxyl group or can provide or receive electricity with free hydroxyl The compound of son pair, includes but are not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc.. Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt%.
Antistatic agent in the auxiliary agent for adding/using can draw the deleterious charge assembled in polymer samples It leads or eliminates, make it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several Antistatic agent：Anionic antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethyl Alcohol amine salt, to nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkane Base dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, N- lauryls- Bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol epoxy It is ethane additive product, fatty acid ethylene oxide addition product, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, sweet Oily mono fatty acid ester；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyene propionamide N- seasons such as ethylenediamine Ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, the preferred lauryl of antistatic agent Trimethyl ammonium chloride, octadecyldimethyl ethoxy quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used is not particularly limited, generally 0.3-3wt%.
Emulsifier in the auxiliary agent for adding/using can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitutes the surface tension between phase, is allowed to form uniform and stable dispersion or emulsion, is preferred for carrying out lotion Polymerized/cross-linked comprising but be not limited only to following any or appoint several emulsifiers：Anionic, such as higher fatty acid salt, alkane Base sulfonate, alkylbenzene sulfonate, Negel, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor Sesame oil sulfuric acid, sulphation butyl ricinoleate salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, as alkylammonium salt, Alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic Type, as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide add At object, fatty acid glyceride, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, alcohol Amine fatty acid amide etc.；Wherein, the preferred neopelex of emulsifier, sorbitan fatty acid ester, triethanolamine are stearic Acid esters (Emulphor FM).Emulsifier used is not particularly limited, generally 1-5wt%.
Dispersant in the auxiliary agent for adding/using enables to solid flocculation group point in mixed with polymers liquid It dissipates and is suspended in liquid for tiny particle, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, simultaneously Also it can prevent the sedimentation and cohesion of particle, be formed and stabilize suspension comprising but be not limited only to following any or appoint several points Powder：Anionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as fat Fat alcohol polyoxyethylene ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Wherein, divide The preferred neopelex of powder, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.Point used Powder dosage is not particularly limited, generally 0.3-0.8wt%.
Colorant in the auxiliary agent for adding/using, can make polymeric articles show required color, Increase surface color and polish comprising but be not limited only to following any or appoint several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium Red, iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalein Cyanines are red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, intellectual circle Blue RSN, slag rhodamine toner, Oil Yellow etc.；Wherein, the selection of colorant, need not be special depending on color sample demand It limits.Colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent for adding/using can make contaminated substance obtain the glittering of similar fluorite Luminous effect comprising but be not limited only to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, Pyrazoline type, benzo oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent Bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of (fluorescent brightener CBS), 4,4-, 2,2- (4,4 ' - Diphenylethyllene) dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002-0.03wt%.
Delustering agent in the auxiliary agent for adding/using when incident light being enabled to reach polymer surfaces, occurs Diffusing reflection generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents：It is heavy Barium sulfate, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc. drop；Wherein, the preferred dioxy of delustering agent SiClx.Delustering agent dosage used is not particularly limited, generally 2-5wt%.
Fire retardant in the auxiliary agent for adding/using, can increase the flame resistance of material comprising but not only limit In following any or several fire retardants：Phosphorus system, as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, Phosphate toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Have Machine halide, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；It is inorganic fire-retarded Agent, such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos Propyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, and one As be 1-20wt%.
Nucleating agent in the auxiliary agent for adding/using can accelerate knot by the crystallization behavior of change polymer Brilliant rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, the raising product transparency, The purpose of the physical mechanical properties such as lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, packet It includes but is not limited only to following any or appoints several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid Sodium, silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, nucleating agent is preferred Silica, benzylidene sorbitol (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
It is good can to ensure that polymer has during film for rheological agent in the auxiliary agent for adding/using Brushability and coating thickness appropriate, prevent storage when solid particle sedimentation, its redispersibility can be improved comprising but It is not limited only to following any or appoints several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, carbonic acid Calcium, lithium chloride, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound is such as hard Resin acid aluminium, aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanic acid Ester derivant, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferably organic swelling of rheological agent Soil, polyethylene wax, hydrophobically modified alkalinity swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used It is not particularly limited, generally 0.1-1wt%.
Thickener in the auxiliary agent for adding/using, can assign the good thixotropy of mixed with polymers liquid and Consistency appropriate, to meet various need such as its stability and application performance during production, storage and use It asks comprising but be not limited only to following any or appoint several thickeners：Lower-molecular substance, such as fatty acid salt, alkyl dimethylamine It is oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, sweet Oily trioleate, coamidopropyl glycine betaine, titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, micro mist Silica, colloidal aluminum, animal protein, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid are total Polymers, polyacrylamide, polyvinyl pyrrolidone, polyethers etc.；Wherein, the preferred hydroxyl coconut oil diethanol amide of thickener, acrylic acid- Methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the auxiliary agent for adding/using can ensure that the flat smooth of polymer coating film is uniform, change Kind film coated surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Poly dimethyl silicon Oxygen alkane, polymethylphenylsiloxane, polyacrylate, organic siliconresin etc.；Wherein, the preferred polydimethylsiloxanes of levelling agent Alkane, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
In the preparation process of dynamic aggregation object, addible auxiliary agent preferred catalyst, initiator, antioxidant, light are stablized Agent, heat stabilizer, chain extender, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.
The addible filler, primarily serves following effect in dynamic aggregation object：1. reducing moulded products Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting polymerization The viscosity of object；3. meeting different performance requirement, polymer material impact strength and compressive strength, hardness, rigidity and mould are such as improved Amount improves wearability, improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning Photostability and chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The addible filler, selected from following any or several fillers：Inorganic non-metallic filler, metal are filled out Material, organic filler.
The addible inorganic non-metallic filler includes but are not limited to following any or appoints several：Calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, carbon nanotube, molybdenum disulfide, slag, flue Ash, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, oil shale powder, Swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass microballoon, foam microspheres, glass Powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, Ceramic fibre, whisker etc..
The addible metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, Powder, nano particle and the fiber of gold etc. and its alloy.
The addible organic filler includes but are not limited to following any or appoints several：Fur, natural rubber Glue, asbestos, shellac, chitin, chitosan, protein, raw lacquer, shell powder, silk, artificial silk, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, chitosan, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
It, can be by any appropriate material hybrid mode known in the art by one in the preparation process of dynamic aggregation object Surely the raw material matched prepares dynamic aggregation object by mixing, and can be interval, semicontinuous or continuous processing form mixing； Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic aggregation object.The hybrid mode packet of use Include but be not limited only to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., wherein it is preferred that Solution is stirred, melting is stirred and melting extrusion.Energy in material mixed process provides form It is limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, injection moulding, mould Molded, tape casting, calendering formation, cast molding.
In the preparation process of dynamic aggregation object, can also add/using the other polymers of the foregoing description, auxiliary agent, fill out Material collectively constitutes dynamic aggregation object compound system, but these add/be not necessarily all necessary using object.
The specific method for preparing dynamic aggregation object, the typically shape by raw material to dissolve or disperse are stirred using solution Formula is stirred mixing in the reactor in respective solvent or in common solvent.In general, hybrid reaction temperature controls At 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, time control is mixed in 0.5-12h, preferably 1-4h.It can incite somebody to action The product obtained after mixing is poured into suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0- 48h obtains polymer samples.Can select during this to retain as needed solvent be made in the form of glue etc. existing for polymer Sample, or selection remove solvent and solid polymer sample existing for the forms such as membranaceous, blocky, foam-like are made.In this approach When preparing dynamic aggregation object, usually also need to that initiator is optionally added in a solvent to cause polymerization in a manner of polymerisation in solution It obtains dynamic aggregation object, or is added dispersant and oil-soluble initiator is configured to suspension with suspension polymerisation or slurry polymerization Mode obtains dynamic aggregation object to cause polymerization, or addition initiator and emulsifier are configured to emulsion with the side of emulsion polymerization Formula obtains dynamic aggregation object to cause polymerization.Used polymerisation in solution, suspension polymerisation, slurry polymerization and emulsion polymerization side Method, is well known to those skilled in the art and widely used polymerization, can be adjusted according to actual conditions, here No longer it is developed in details.
Used solvent, should carry out according to actual conditions such as reactant, product and reaction process in above-mentioned preparation method Selection includes but are not limited to following any solvent or appoints the mixed solvent of several solvents：Deionized water, acetonitrile, acetone, fourth Ketone, benzene,toluene,xylene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, methanol, ethyl alcohol, chloroform, dichloromethane Alkane, 1,2- dichloroethanes, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, acetic acid isopropyl Ester, n-butyl acetate, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, Phosphate buffer solution, borate buffer solution etc.；It is preferred that deionized water, toluene, chloroform, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene Furans, dimethylformamide, phosphate buffer solution.In addition, solvent is also selected from oligomer, plasticizer, ionic liquid；Described Oligomer includes but are not limited to polyethylene glycol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid Body paraffin etc.；The plasticizer can be selected from classification described in the plasticizer in addible auxiliary agent, and which is not described herein again；It is described Ionic liquid be generally made of organic cation and inorganic anion, cation is usually that alkyl quaternary ammonium ion, alkyl quaternary are seen Imidazol ion, the alkyl-substituted pyridinium ions of N- etc. that ion, 1,3- dialkyl group replace；Anion is usually halide ion, four Fluoro boron acid ion, also has CF at hexafluorophosphoricacid acid ions3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、 (CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -Deng.Wherein, dynamic aggregation is prepared using deionized water Object simultaneously selects when being retained, and can obtain hydrogel；Dynamic aggregation object is prepared using organic solvent and selects to be retained When, organogel can be obtained；When preparing dynamic aggregation object using oligomer and selecting to be retained, oligomer can be obtained Swell gel；When preparing dynamic aggregation object using plasticizer and selecting to be retained, plasticizer swell gel can be obtained；Profit When preparing dynamic aggregation object with ionic liquid and selecting to be retained, ionic liquid swell gel can be obtained.
In above-mentioned preparation method, the compound liquid concentration configured is according to the structure of selected reactant, molecular weight, dissolving Depending on degree and required dispersity, it is not particularly limited, preferred a concentration of 0.1~10mol/L of compound liquid, more preferably For 0.1~1mol/L.
It is stirred the specific method for preparing dynamic aggregation object using melting, typically directly stirs raw material in the reactor It is stirred reaction after mixing mixing or heating melting, such mode is generally gas, liquid or lower melting-point solid in raw material In the case of use.In general, the control of hybrid reaction temperature is at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixing is stirred Time control is mixed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, in 0- 150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, polymer samples are obtained.Dynamic aggregation object is prepared in this approach When, it usually also needs to be optionally added into a small amount of initiator to cause in a manner of melt polymerization or gas-phase polymerization polymerization and obtains dynamic Polymer.The method of its used melt polymerization, gas-phase polymerization, is well known to those skilled in the art and is widely used Polymerization, can be adjusted according to actual conditions, no longer be developed in details here.
The specific method of dynamic aggregation object is mixed with using melting extrusion, be typically add the raw material into extruder into Row squeezes out blending reaction, and extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be cut into conjunction after direct tape casting Suitable size either carries out obtained extrusion sample to utilize injection molding machine or moulding press to carry out sample preparation after being crushed.Injection temperature is 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature be 0-280 DEG C, preferably 25-150 DEG C, more It is preferred that 25-80 DEG C, clamp time 0.5-60min, preferably 1-10min, the preferred 4-15MPa of molding pressure.Batten can be placed in In suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, final polymer samples are obtained.
In the preparation process of dynamic aggregation object, mole of selected inorganic compounds of boron and (poly-) silicone compounds Equivalent proportion should be at range appropriate, preferably 0.1~10 range, more preferable 0.3~3 range, more preferable 0.8~1.2 Range.In actual fabrication process, those skilled in the art can be adjusted according to actual needs.
In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The dynamic aggregation physical performance is adjustable on a large scale, has broad application prospects, in military aerospace equipment, function Coating and the fields such as coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material all have important answer With.
By using dilatancy, dynamic possessed by dynamic aggregation object, making damping shock absorber can be applied to, used In the vibration isolation of various motor vehicles, mechanical equipment, bridge, building, polymer material can dissipate big when vibrated Energy plays damping, to effectively mitigate vibrations；Also it can be applied to buffering package as energy-absorbing buffering material Material, athletic protective article, the police protective materials of surge guard product and army etc., to reduce article or human body outside Suffered vibrations and impact under force effect include the shock wave etc. of noise and explosion generation.Utilize the dynamic of boric acid estersil key Property, it can also be used as shape-memory material, when the external force is removed, the deformation energy that material generates in loading procedure Enough restored；By dynamic reversibility possessed by dynamic aggregation object and rate of stressing dependence, stress sensitive type is prepared Polymer material, a part can be applied to prepare have stress/strain response magic toy and body-building material, also can be used In the speed lockup's device for preparing road and bridge, can be also used for making antidetonation shear plate or pulsating stress carrying tool, or For making stress monitoring sensor.
The had dynamic of dynamic aggregation object is made full use of, the binder with self-repair function can be prepared, is applied In the gluing of various types of materials, bulletproof glass squeegee also can be used as；It can also be used for preparing the polymer envelope with good plasticity Stifled glue, can design and prepare the scratch resistant coatings with self-repair function, to extend the service life of coating, realize to base The long-effective corrosion of body material is protected.Huge application potential is shown in the fields such as military project, space flight, electronics, bionical.
It is carried out using inorganic boric acid estersil key as key can be sacrificed in use, a large amount of energy can be absorbed and assign polymer Material is with excellent toughness, it is hereby achieved that the polymer material that toughness is splendid, is widely used in military affairs, space flight, movement, energy The fields such as source, building.
Dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specific implementation Example is present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
End hydroxy butadiene (HTPB) and toluene di-isocyanate(TDI) (2,4-TDI) are sufficiently mixed, add a small amount of third Triol is as crosslinking agent, NCO in control reaction：OH is about 1.2:1, i.e. 2, the 4-TDI amount of skipping over, covalent cross-linking obtain a kind of side group Polyurethane (molecular weight about 18000) containing double bond.
The above-mentioned side groups of 12.8g are contained to polyurethane (molecular weight about 18000), the 1.5g 6- mercapto propyl trimethoxies of double bond Silane and 0.7g 1,12- dimercaptos dodecanes according to double bond and the compound of two sulfydryls molar ratio 22:20:1 mixing, adds Enter the photoinitiator benzoin dimethylether (DMPA) of 0.2wt% and be placed on ultraviolet radioactive 4h in UV crosslinking instrument after stirring fully, A kind of polyurethane containing common covalent cross-linking is prepared.
By the above-mentioned polyurethane containing common covalent cross-linking of 35.1g, the ends 12.0g silicone hydroxyl polydimethyl siloxane fluid and 4.8g boron Sour trimethyl is sufficiently mixed, and is added 0.5g Graphene powders and is warming up to 80 DEG C after mixing after stirring is sufficiently mixed, is added The deionized water of 4ml, then it is added dropwise to a small amount of acetic acid, polymerisation is carried out under stirring, is prepared a kind of containing general The dynamic aggregation object of logical covalent cross-linking and boric acid estersil key.
There is the polymeric articles excellent toughness, electric conductivity the change of sensitivity can be generated with pressure and tension variations Change, there is power sensing function, can be used as force snesor.
Embodiment 2
First by a certain amount of trimethylolpropane tris (2- mercaptoacetates) and 1,6- hexadienes according to sulfydryl and double bond Molar ratio is 2:1 mixing, is placed on ultraviolet radioactive 2h in UV crosslinking instrument, obtains a kind of polymerization containing slight common covalent cross-linking Object and remaining a certain amount of trimethylolpropane tris (2- mercaptoacetates), as a kind of prepolymer.
By trimethylborate and dimethyl methyl oxygroup -3- butylene silane according to molar ratio 1:3 mixing, are heated to 60 DEG C and pass through After stirring is dissolved, it is added a small amount of water the reaction was continued 4h, obtains a kind of trivinyl compound containing boric acid estersil key 2a。
Silicone hydroxyl blocks and side group carries the organopolysiloxane (molecular weight about 2500) and 2,6- bis--of terminal olefin group Tert-butyl -4- tolyls dibutyl ortho-boric acid ester according to terminal siloxane and borate molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 6ml is added, polymerisation is carried out under stirring, one kind is prepared and contains boric acid The organopolysiloxane of estersil key.
By the above-mentioned prepolymers of 16.7g, the above-mentioned organopolysiloxanes containing boric acid estersil key of 1.4g compounds 2a and 9.8g It is sufficiently mixed, is placed on ultraviolet radioactive 8h in UV crosslinking instrument, obtain a kind of dynamic containing common covalent cross-linking and boric acid estersil key State polymer.
The polymeric articles can as with certain selfreparing and with tear resistance sheet material or coating use.
Embodiment 3
(1) by 3- aminopropyltriethoxies dimethoxysilane and Adipoyl Chloride according to molar ratio 2:1 mixing, using triethylamine as Catalyst reacts in anhydrous methylene chloride, and disiloxane compound is prepared.
Hold poly- (dimethyl-methylphenyl) siloxanes of silicone hydroxyl, above-mentioned disiloxane compound, isopropanol pinacol boric acid Ester is according to Si-OH, Si-OCH3The molar ratio 1 of group and B-OR groups:1:2 mixing, it is water-soluble to be added dropwise to 20% a small amount of acetic acid Liquid after being stirred evenly under the conditions of 50 DEG C, reacts 8h, a kind of dynamic aggregation object containing boric acid estersil key is prepared, as 1st network polymer.
(2) N, N '-methylene-bisacrylamide, Lu's succinimide mercaptans, trimethylolpropane tris (3-thiopropionate) according to Molar ratio 20:20:1 mixing, is added to the peace that 0.2wt% is added in 120wt% plasticizer epoxidized methyl acetorieinoleates The fragrant double methyl ethers (DMPA) of breath, add 30mg graphenes, the 1st network polymer of quality such as swell in, and ultrasonic disperse pours into folder Have in the glass board mould of silica gel pad, be placed on ultraviolet radioactive 8h in UV crosslinking instrument, one kind containing common covalent cross-linking, skeleton The organogel that the epoxidized methyl acetorieinoleate of hydrogen bond group and boric acid estersil key is swollen.
For the modulus of the organogel of epoxidized methyl acetorieinoleate swelling prepared by the embodiment in 22kPa, strain can To reach 16 times, fracture strength is in 89kPa.This organogel can be used for preparing airborne and air-drop defense of resistance to impact material Material.
Embodiment 4
(1) by vinyl acetic acid and 2,6- diamino-pyridines according to molar ratio 2:1 reaction, is made compound 4a.
Two mercaptan of 1,3- diphenyl propanes -2,2- and compound 4a, triallylamine are according to molar ratio 9:6:2 are mixed, It is placed on ultraviolet radioactive 8h in UV crosslinking instrument, obtains a kind of polymer containing skeleton hydrogen bond group and common covalent cross-linking, is made For the 1st network polymer.
(2) by boric acid and acrylic dimethylchlorosilane according to molar ratio 1:3 mixing, using triethylamine as catalyst, 80 12h is reacted at DEG C, and the boric acid estersil compound 4b that end carries double bond is prepared.
Two mercaptan of 16g polyethers is added in three-necked flask, 5.4g above-mentioned ends carry the boric acid estersil compound 4b of double bond It is uniformly mixed, fully swells in the 1st network polymer, then be placed on ultraviolet radioactive 8h in UV crosslinking instrument, obtain one kind and contain The dual network interpenetrating dynamic aggregation object of common covalent cross-linking and boric acid estersil key.
(3) end silicone hydroxyl polydimethyl siloxane fluid, three sec-butyl borates according to silicone hydroxyl and borate molar ratio 1:1 is mixed It closes, a small amount of water, 2g white carbons, 2g titanium dioxides, 1.3g di-iron trioxides is added, fully swells in above-mentioned binary latex interpenetrating polymerization In object, after being stirred evenly under the conditions of 50 DEG C, 6h is reacted, is prepared a kind of containing common covalent cross-linking and boric acid estersil key Ternary network interpenetrating dynamic aggregation object.
The polymeric articles can be used for making antidetonation shear plate or pulsating stress carrying tool.
Embodiment 5
(1) limonene oxide extracted from orange peel, and 100psi carbon dioxide, under the catalytic action of beta-diimine zinc Polymerisation occurs, obtains makrolon PLimC.
By above-mentioned makrolon PLimC and N- [(2- mercaptoethyls) carbamyl] propionamide, two (2- mercaptoethyls) oneself Two acid esters are 10 according to double bond group and sulfydryl ratio:9:1 mixing, is added the AIBN of 0.6wt%, is made and is contained by click-reaction There is the makrolon (molecular weight about 10000) of common covalent cross-linking and silicone hydroxyl presoma.
Weigh the makrolon of the above-mentioned side group silicone hydroxyl presomas of 24g, the poly- methyl trifluoro propyl-of 38g silicone hydroxyls sealing end Methylsiloxane (molecular weight 8000) and 5g tri- (2- methoxy ethyls) borate are thoroughly mixed uniformly, are warming up to 80 DEG C Afterwards, the deionized water of 10ml is added, polymerisation is carried out under stirring, be prepared it is a kind of containing common covalent cross-linking and The dynamic aggregation object of boric acid estersil key, as the 1st network polymer.
(2) two mercaptan of 15g polyethers is added in three-necked flask, 2.0g triallylamines swell in the 1st network polymer In, 3.2g di-iron trioxides, 0.2g carbon nanotubes is added, then be placed on ultraviolet radioactive 8h in UV crosslinking instrument, obtains one kind and contain The dual network interpenetrating dynamic aggregation object of common covalent cross-linking and boric acid estersil key.
The polymer samples have larger sticky and very good tensile toughness, can largely be stretched and Not broken (elongation at break is up to 600%).In the present embodiment, can make polymer as electronic package material or adhesive With, can to the fine cracks of appearance carry out selfreparing, can avoid material destruction and gas leakage.
Embodiment 6
(1) 3- isocyanides acid propylene and 3- hydroxyl -1- propylene equimolar ratios are reacted, amino first of the both ends with vinyl is made Ester compound 6a.
Using Tert-butyl Methacrylate and compound 6a as monomer, the molar ratio for controlling the two is 10:1, pass through free radical A kind of common covalent cross-linking polymer (molecular weight is about 7500) containing skeleton hydrogen bond group is made in polymerization, as the 1st network Polymer.
(2) it is single with methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and two three (1,2- propylene glycol) diacrylates of contracting Body, the molar ratio for controlling the two are 10:1, by free radical polymerization be made methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and The copolymer (molecular weight is about 6000) of two three (1,2- propylene glycol) diacrylates of contracting.
By above-mentioned methacrylic acid 3- (trimethoxy silicon substrate) propyl ester, end silicone hydroxyl polydimethyl siloxane fluid and two contracting three (1, 2- propylene glycol) diacrylate ester copolymer and trimethylborate be according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 is mixed It closes, fully swells in etc. in the 1st network polymer of quality, add the nano silicon dioxide of 5wt% grain sizes 25nm, be warming up to 80 DEG C after mixing, and the deionized water of 10ml is added, and polymerisation is carried out under stirring, is prepared a kind of containing general The dynamic aggregation object of logical covalent cross-linking and boric acid estersil key.
The polymer is prepared into film, shows more excellent comprehensive performance, there is certain tensile strength and good Good tear resistance, and can largely be stretched.Such dynamic aggregation object can be applied to prepare function film, or It can be used as the pad pasting of automobile and furniture, also can be used as stretch wrappers and used, very scratch-resistant.
Embodiment 7
(1) it is single with methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and trimethylol-propane trimethacrylate Body, the molar ratio for controlling the two are 20:1, by free radical polymerization be made methacrylic acid 3- (trimethoxy silicon substrate) propyl ester and The copolymer of trimethylol-propane trimethacrylate (molecular weight is about 2500).
Polymethyl-benzene base-the dimethyl siloxane and 2.7g boric acid front threes that the above-mentioned copolymers of 25g, 16g silicone hydroxyls are blocked Ester mixes, and is warming up to 80 DEG C after mixing, the deionized water of 12ml is added, polymerisation is carried out under stirring, prepares A kind of dynamic aggregation object containing common covalent cross-linking and boric acid estersil key is obtained, as the 1st network polymer.
(2) by boric acid and dimethyl methyl oxygroup -3- heptene silane according to molar ratio 1:3 mixing, are heated to 60 DEG C by stirring It mixes after being dissolved, is added a small amount of water the reaction was continued 4h, obtain a kind of trivinyl compound 7a containing boric acid estersil key.
Silicone hydroxyl blocks and side group carries the organopolysiloxane (molecular weight about 2000) and 2,6- bis--of terminal olefin group Tert-butyl -4- tolyls dibutyl ortho-boric acid ester according to terminal siloxane and borate molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 6ml is added, polymerisation is carried out under stirring, one kind is prepared and contains boric acid The organopolysiloxane of estersil key.
First by 0.8g diallyl adipates and 3.7g trimethylolpropane tris (2- mercaptoacetates) in UV crosslinking instrument Middle ultraviolet radioactive 8h carries out pre-polymerization 1h, and it is above-mentioned organic poly- containing boric acid estersil key then to add 2.6g compounds 7a and 12g Siloxanes above-mentioned (molecular weight about 25000) is sufficiently mixed, and is swollen in the 1st network polymer, is placed in UV crosslinking instrument purple External radiation 8h obtains a kind of dynamic aggregation object containing common covalent cross-linking and boric acid estersil key.
The polymeric articles can be used for preparing a kind of police protective materials of army.
Embodiment 8
(1) it by 1,3,5- tri- (bromomethyl) benzene and sodium azide in DMF solution, stirs 2 days, it is (folded to be made 1,3,5- tri- N-methyl) benzene.
Adipic acid dipropargyl ester and (azido-methyl) benzene of 1,3,5- tri- are according to molar ratio 3:2 mixing, are added relative to list Catalyst CuBr (the PPh of body 0.1wt%3)3With three [(1- benzyls -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), stirring After being sufficiently mixed, 4h is reacted at 60 DEG C, a kind of polymer containing common covalent cross-linking is obtained, as the 1st network polymer.
(2) methyl -3,3,3- trifluoro propyls polysiloxanes hydroxy-end capped 50g, the ends 20g carry trimethoxy silicon group Four arms PEG (molecular weight is about 12000) and 22g trimethylborates mixing, be warming up to 80 DEG C after mixing, add The deionized water of 4ml carries out polymerisation under stirring, is prepared a kind of poly- containing the crosslinked dynamic of boric acid estersil key Close object.It this is contained into the crosslinked dynamic aggregation object of boric acid estersil key is added in small-sized extruder and carry out extrusion blending, squeeze out temperature Degree is 120 DEG C, after obtained extrusion batten is granulated, obtains elastic little particle.
This elasticity little particle is scattered in a solvent in the 1st network polymer, is subsequently placed in 50 DEG C of baking ovens and carries out for 24 hours It except solvent, is cooled to is placed at room temperature for 30min later, obtain a kind of dynamic aggregation containing common covalent cross-linking and boric acid estersil key Object.
The polymeric articles show good viscoplasticity, have good isolation vibrations and stress buffer effect, together When also show excellent hydrolytic resistance.
Embodiment 9
(1) four mercaptoacetate of pentaerythrite and diallyl adipate are mixed, the ratio of control three's molal quantity is 1:2, it pours into the glass board mould for accompanying silica gel pad, is placed on ultraviolet radioactive 4h in UV crosslinking instrument, be made a kind of containing general The crosslinked polymer of valence in all, as the 1st network polymer.
(2) using BPO as initiator, methyl vinyl diethoxysilane and low density polyethylene (LDPE) are subjected to graft reaction system Obtain a kind of grafted polyethylene that side group contains diethoxy silane group.
Bis- chloro- 1,1,3,3,5,5,7,7,9,9,11,11- of 1,11-, ten dimethyl, six siloxanes, above-mentioned side group contain diethyl The grafted polyethylene and trimethylborate of oxysilane group are according to Si-Cl, Si-OCH2CH3Group and B-OCH3Mole of group Than 1:3:4 mixing, are added a small amount of water, 2.3g white carbons, 4.1g titanium dioxides, after being stirred evenly under the conditions of 50 DEG C, react 6h, One kind is prepared and contains the crosslinked dynamic aggregation object of boric acid estersil key.
Above-mentioned be added in small-sized extruder containing the crosslinked dynamic aggregation object of boric acid estersil key is subjected to extrusion blending, is squeezed It is 120 DEG C to go out temperature, after obtained extrusion batten is granulated, obtains elastic little particle.By this elastic little particle in solvent In be scattered in the 1st network polymer, be subsequently placed in 50 DEG C of baking ovens carry out for 24 hours remove solvent, be cooled to be placed at room temperature for later 30min obtains a kind of dynamic aggregation object containing common covalent cross-linking and boric acid estersil key.
The dynamic aggregation object mechanical property is strong, excellent shock resistance, can prepare a kind of defense of resistance to impact pad use.
Embodiment 10
(1) using n-BMA and trimethylol-propane trimethacrylate as monomer, rubbing for the two is controlled You are than being 60:1, the AIBN of 3mol% is added as initiator, n-BMA and three are made by free radical polymerization The copolymer (molecular weight is about 8000) of methylolpropane trimethacrylate containing common covalent cross-linking net to get to one kind The polymer of network.
(2) 5- chlorine amyl dimethyl methoxy silanes and boron triethyl acid esters are mixed according to equimolar ratio, is heated to 60 After DEG C being dissolved by stirring, a small amount of water reaction 3h is added, obtains a kind of boric acid ester compound containing boric acid estersil key.
By 20g dimethyl silicone polymers (molecular weight about 4000), the polyethylene glycol (molecule that the both ends 15g are silicone hydroxyl sealing end 3000) amount is about mixed with the above-mentioned boric acid ester compounds containing boric acid estersil key of 8g, it is 50nm that a small amount of water and 0.4g grain sizes, which is added, Talcum powder, after being stirred evenly under the conditions of 80 DEG C, react 6h, a kind of non-crosslinked dynamic containing boric acid estersil key is prepared Polymer.This non-cross-linked polymer for containing boric acid estersil key is swollen in into the network polymer containing common covalent cross-linking, is obtained To a kind of dynamic aggregation object containing common covalent cross-linking and boric acid estersil key.
The polymeric articles show good viscoplasticity, have good isolation vibrations and stress buffer effect, can To be used as a kind of elastic buffer gasket.
Embodiment 11
(1) limonene oxide extracted from orange peel, and 100psi carbon dioxide, under the catalytic action of beta-diimine zinc Polymerisation occurs, obtains makrolon PLimC.
It weighs the above-mentioned makrolon PLimC of 24g (molecular weight about 6000) and 1.6g bis- (2- mercaptoethyls) adipate ester is pressed It is 20 according to double bond group and sulfydryl ratio:1 mixing, is added the AIBN of 0.6wt%, one kind, which is prepared, by click-reaction contains The network polymer of common covalent cross-linking.
(2) 3- chloropropyls dimethyl methoxy silane and boric acid are mixed according to equimolar ratio, are heated to 60 DEG C and are passed through stirring After being dissolved, a small amount of water reaction 3h is added, obtains a kind of boronic acid compounds containing boric acid estersil key.
By 2.0g 4,4'- connection silicon benzene alcohol, bis- chloro- 1,1,3,3,5,5,7,7,9,9,11,11- of 6.5g 1,11-, ten diformazans Six siloxanes of base and the above-mentioned boronic acid compounds mixing containing boric acid estersil key of 5.2g, are heated to 80 DEG C, a small amount of water are then added The reaction was continued 8h, obtains a kind of non-crosslinked dynamic aggregation object containing boric acid estersil key.This is contained to the non-friendship of boric acid estersil key Linked polymer swells in the network polymer containing common covalent cross-linking, obtains one kind and containing common covalent cross-linking and boric acid estersil The dynamic aggregation object of key.
The polymeric articles can be used for making antidetonation shear plate or pulsating stress carrying tool.
Embodiment 12
(1) two mercaptan of 25g polyethers, 10g N, N '-methylene-bisacrylamide, tri- allyls of 1.5g are added in three-necked flask Base amine is placed on ultraviolet radioactive 8h in UV crosslinking instrument, a kind of polymer containing common covalent cross-linking is obtained, as the 1st network Polymer.
(2) 0.8g diallyl adipates and 3.7g trimethylolpropane tris (2- mercaptoacetates) are placed on UV crosslinking Ultraviolet radioactive 8h in instrument obtains a kind of polymer containing common covalent cross-linking, as the 2nd network polymer.
(3) 18- chlorine octadecyldimethyl methoxy silanes and trimethylborate are mixed according to equimolar ratio, is heated to After 60 DEG C are dissolved by stirring, a small amount of water reaction 3h is added, obtains a kind of borate chemical combination containing boric acid estersil key Object.
By polysiloxane block polyethylene glycol (molecular weight about 12000) that the both ends 18g are silicone hydroxyl sealing end and 5g is above-mentioned contains There is the boric acid ester compound of boric acid estersil key to mix, a small amount of water is added, after being stirred evenly under the conditions of 80 DEG C, reacts 6h, prepare Obtain a kind of non-crosslinked dynamic aggregation object containing boric acid estersil key.
By a kind of above-mentioned nano silicon dioxide point of the non-crosslinked dynamic aggregation object containing boric acid estersil key and grain size 25nm It dissipates in the 1st network polymer and the 2nd network polymer, obtains a kind of dynamic containing common covalent cross-linking and boric acid estersil key Polymer.
The polymeric articles can be used for making damping shock absorber, be applied to various motor vehicles, mechanical equipment.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (12)

1. a kind of dynamic aggregation object with hybrid cross-linked structure, which is characterized in that wherein include at least one common covalently friendship Networking network, and at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein include dynamic simultaneously The covalent inorganic boric acid estersil key of state, wherein the dynamic covalently any one B atom and three-O- in inorganic boric acid estersil key Connection, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms are connected by linker L, The different Si atoms being based partially on simultaneously in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The company Base L is met, the carbon atom on dynamic covalent polymer main chain backbone is contained；The linker Y, covalently in dynamic The structure of main polymer chain skeleton only contains (poly-) siloxane unit.
2. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer only there are one network, in the network contains common covalent cross-linking and dynamic simultaneously, and covalently inorganic boric acid estersil key is handed over Connection, wherein common covalent cross-linking reaches its gel point or more and its cross-linked network skeleton is carbochain or carbon heterochain structure；Wherein, Covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and to be based on different B former for which part Different Si atoms in the B-O-Si dynamic covalent bonds of son are connected by linker L, while being based partially on the B-O- of different B atoms Different Si atoms in Si dynamic covalent bonds are connected by linker Y；The linker L contains covalently poly- in dynamic The carbon atom on owner's chain backbone, the linker Y are closed, the structure on dynamic covalent polymer main chain backbone contains only There is (poly-) siloxane unit.
3. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer is containing there are two networks；Common covalent cross-linking is contained only in 1st network, common covalent cross-linking reaches its gel point or more And its covalent cross-linking network skeleton is carbochain or carbon heterochain structure；With the covalent inorganic boric acid estersil key-shaped of dynamic in 2nd network At crosslinking reach its gel point or more, without common covalent cross-linking more than gel point, wherein the covalent Inorganic Boron of dynamic Any one B atom is connect with three-O- in sour estersil key, and B-O-Si dynamic of the which part based on different B atoms is covalent Different Si atoms in key are connected by linker L, while being based partially in the B-O-Si dynamic covalent bonds of different B atoms not It is connected by linker Y with Si atoms；The linker L contains the carbon on dynamic covalent polymer main chain backbone Atom, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.
4. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer is containing there are two networks；Contain common covalent cross-linking and dynamic covalently inorganic boric acid estersil key in 1st network simultaneously Crosslinking, wherein common covalent cross-linking reaches its gel point or more and its cross-linked network skeleton is carbochain or carbon heterochain structure；2nd Common covalent cross-linking is contained only in network, is free of the dynamic covalently inorganic boric acid estersil key；Wherein, at least one described common total Valence cross-linked network skeleton is carbochain or carbon heterochain structure；Wherein, covalently any one B is former in inorganic boric acid estersil key for the dynamic Son is connect with three-O-, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms pass through company It meets base L to be connected, while being based partially on the different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms and passing through linker Y phases Even；The linker L, contains the carbon atom on dynamic covalent polymer main chain backbone, the linker Y, Structure on dynamic covalent polymer main chain backbone only contains (poly-) siloxane unit.
5. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer is containing there are two networks；1st network and the 2nd network contain common covalent cross-linking and the covalent Inorganic Boron of dynamic simultaneously Sour estersil key crosslinking, wherein common covalent cross-linking reaches its gel point or more, and at least one common covalent cross-linking net Network skeleton is carbochain or carbon heterochain structure, but described the 1st and the 2nd network are different.Wherein, the covalent inorganic boric acid silicon of the dynamic Any one B atom is connect with three-O- in ester bond, and in B-O-Si dynamic covalent bonds of the which part based on different B atoms Different Si atoms be connected by linker L, while different Si being based partially in the B-O-Si dynamic covalent bonds of different B atoms Atom is connected by linker Y；The linker L contains the carbon atom on dynamic covalent polymer main chain backbone, The linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.
6. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer contains at least one network, and common covalent cross-linking is only contained in those networks, at least one described common covalent Cross-linked network skeleton is carbochain or carbon heterochain structure, and with the covalent inorganic boric acid estersil key cross-linked polymer of dynamic with granulated Formula is dispersed in the network；Wherein, covalently any one B atom and three-O- connect the dynamic in inorganic boric acid estersil key It connects, and the different Si atoms in B-O-Si dynamic covalent bonds of the which part based on different B atoms are connected by linker L, The different Si atoms being based partially on simultaneously in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The company Base L is met, the carbon atom on dynamic covalent polymer main chain backbone is contained, the linker Y is covalent in dynamic Structure on main polymer chain skeleton only contains (poly-) siloxane unit.
7. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer is contained only there are one network, and common covalent cross-linking, the common covalent cross-linking network skeleton are only contained in the network For carbochain or carbon heterochain structure, and the non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed in the network In；Wherein, covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and which part base Different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker L, while being based partially on different B Different Si atoms in the B-O-Si dynamic covalent bonds of atom are connected by linker Y；The linker L, contains and is in Carbon atom on dynamic covalent polymer main chain backbone, the linker Y, on dynamic covalent polymer main chain backbone Structure only contain (poly-) siloxane unit.
8. a kind of dynamic aggregation object with hybrid cross-linked structure according to claim 1, which is characterized in that the dynamic Covalent polymer contains there are two network, common covalent cross-linking is contained only in the 1st network and the 2nd network, and at least one described Common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；1st network and the 2nd network are identical or different, preferably different； The non-cross-linked polymer containing the covalent inorganic boric acid estersil key of dynamic is dispersed at least one of which network；Wherein, described Any one B atom is connect with three-O- in the covalent inorganic boric acid estersil key of dynamic, and which part is based on different B atoms B-O-Si dynamic covalent bonds in different Si atoms be connected by linker L, while being based partially on the B-O-Si of different B atoms Different Si atoms in dynamic covalent bond are connected by linker Y；The linker L contains in dynamic covalently polymerization Carbon atom on owner's chain backbone, the linker Y, the structure on dynamic covalent polymer main chain backbone only contain (poly-) siloxane unit.
9. a kind of dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-8, feature exist In, or containing its composition with following any character：Gel, ordinary solid, elastomer, foam.
10. a kind of dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-8, feature exist In, composition recipe ingredient further include it is following any or appoint it is several can additive or usable object：Other polymers help Agent, filler；
Wherein, the other polymers are selected from following any or appoint several：Natural polymer, synthetic resin, conjunction At rubber, synthetic fibers；
Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, heat are steady Determine agent, crosslinking agent, curing agent, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation Agent, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickening Agent, levelling agent；
Wherein, the filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.
11. a kind of dynamic aggregation object with hybrid cross-linked structure according to any one of claim 1-8, feature exist In applied to following product：Damper, padded coaming, defense of resistance to impact material, athletic protective article, army and police's protective article, Self-repairability coating, self-repairability plank, self-repairability binder, bulletproof glass squeegee, toughness material, shape memory material Material, sealing element, toy, force snesor.
12. a kind of energy-absorbing method, which is characterized in that provide a kind of dynamic aggregation object with hybrid cross-linked structure or its composition simultaneously Energy-absorbing is carried out using it as energy-absorbing material, wherein the dynamic aggregation object includes at least one common covalent cross-linking network, and And at least one common covalent cross-linking network skeleton is carbochain or carbon heterochain structure；Wherein include that dynamic is covalently inorganic simultaneously Boric acid estersil key, wherein covalently any one B atom is connect the dynamic with three-O- in inorganic boric acid estersil key, and wherein The different Si atoms being based partially in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker L, are based partially on simultaneously Different Si atoms in the B-O-Si dynamic covalent bonds of different B atoms are connected by linker Y；The linker L, contains Carbon atom on dynamic covalent polymer skeleton；The linker Y is in the structure of dynamic covalent polymer skeleton Only contain (poly-) siloxane unit.
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