CN108341955A - A kind of dynamic aggregation object or composition and its application with hydridization bonding structure - Google Patents

A kind of dynamic aggregation object or composition and its application with hydridization bonding structure Download PDF

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CN108341955A
CN108341955A CN201710056040.1A CN201710056040A CN108341955A CN 108341955 A CN108341955 A CN 108341955A CN 201710056040 A CN201710056040 A CN 201710056040A CN 108341955 A CN108341955 A CN 108341955A
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dynamic
hydrogen bond
key
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inorganic
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不公告发明人
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Xiamen iron cloth Mstar Technology Ltd.
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Weng Qiumei
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Priority to CN201710056040.1A priority Critical patent/CN108341955A/en
Priority to PCT/CN2018/072455 priority patent/WO2018137505A1/en
Publication of CN108341955A publication Critical patent/CN108341955A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a kind of dynamic aggregation object or composition with hydridization bonding structure, it includes have the inorganic boric acid estersil key of dynamic, optional Inorganic Boron oxygen boron key and supermolecule hydrogen bond.The inorganic boric acid estersil key of dynamic and optional Inorganic Boron oxygen boron key have been carried out orthogonal combination by the dynamic aggregation object with supermolecule hydrogen bond, make full use of the dynamic reversibility different with the two has been played, the functional characteristics such as excellent stimulating responsive, self-repairability are obtained, especially good energy-absorbing effect.The dynamic aggregation object can be widely used for making damping, buffering material, defense of resistance to impact material, self-repair material, toughness material etc..

Description

A kind of dynamic aggregation object or composition and its application with hydridization bonding structure
Technical field
The present invention relates to intelligent polymer fields, and in particular to a kind of tool being made of dynamic covalent bond and supermolecule hydrogen bond By hydridization bonding structure dynamic aggregation object or form and its application.
Background technology
Into after 21 century, scientific and technical progress and expanding economy propose polymer and its material higher It is required that polymer also on the basis of basic performance, continues to develop, polymer towards the direction of functionalization, intelligence, fining Material is also answered from structural material to light, electricity, sound, magnetic, biomedicine, bionical, catalysis, substance separation and energy transformer equivalent Functional material Directional Extension, there is a series of such as separation materials, biomaterial, intellectual material, energy-accumulating material, light guide material Material, nano material, electronic information material etc. have the novel polymer material of functional effect.Polymer architecture and performance are closed The research of system, is also entered by macroscopic view microcosmic, is entered quantitative from qualitative, is entered dynamic by static state, be done step-by-step in MOLECULE DESIGN water It is synthesized on flat and prepares the polymer that can reach desired function.
Traditional polymer is generally made of common covalent bond, and common covalent bond is due to higher bond energy and thermostabilization Property, therefore polymer is also lacking dynamic with good stability and mechanical performance while.And dynamic covalent bond is one Can occur under fixed condition controllable reversible reaction a kind of chemical bond, it be it is a kind of than non-covalent bond stablize, relatively weak is total to Valence link, by changing extraneous condition or Dynamic Fracture and the formation of covalent bond spontaneously may be implemented.Dynamic covalent bond is drawn Enter polymer, is a kind of feasible method forming novel dynamic aggregation object.But common dynamic covalent bond such as Deere think of-Alder Reaction product, oxynitrides etc. generally require to be broken at high temperature, and side reaction is serious.How dynamic is obtained Performance is strong and controllable, system that is having a wide range of application, then is still a problem of the prior art.
Invention content
The present invention is directed to above-mentioned background, provides a kind of dynamic aggregation object or composition with hydridization bonding structure, wraps It will be moved containing the inorganic boric acid estersil key of dynamic, optional Inorganic Boron oxygen boron key and supermolecule hydrogen bond, the dynamic aggregation object or composition The inorganic boric acid estersil key of state and optional Inorganic Boron oxygen boron key have carried out orthogonal combination with supermolecule hydrogen bond, make full use of and send out Its different dynamic reversibility is waved.The dynamic aggregation object or composition have excellent dynamic reversibility, and reflect Stimulating responsive, plasticity, self-repairability, recuperability, can the functional characteristics such as re-workability, while good suction can be obtained It can property and toughness.
The present invention is achieved by following technical solution：
A kind of dynamic aggregation object or composition with hydridization bonding structure, wherein comprising with the inorganic boric acid estersil key of dynamic (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond group, the hydrogen are carried on dynamic aggregation object molecule wherein at least described in part Key group participates in forming hydrogen bond.
In embodiments of the present invention, hydrogen bond group is carried at least partly in dynamic aggregation object molecule, preferably former with B It is connected with group and/or segment with hydrogen bond group on Si atoms on the polysiloxane chain of son connection.
In embodiments of the present invention, other compositions include but not limited to other polymers, small molecule, filler, wherein Hydrogen bond group can also be carried.
In an embodiment of the invention, dynamic aggregation object or group become non-crosslinking structure, wherein in inorganic boric acid Also the cross-linked structure of gel point or more is not up under estersil key, optional Inorganic Boron oxygen boron key and hydrogen bond collective effect.Wherein Including including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, all dynamic covalent bonds are not enough to form gel point or more Dynamic covalent cross-linking；And hydrogen bond action is also not enough to form the hydrogen bond crosslinks of gel point or more；Dynamic covalent bond and hydrogen bond are made With the sum of be also not enough to form the cross-linked structure of gel point or more.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein dynamic aggregation object In comprising including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, be unable to reach the covalent cross-linking of gel point or more；Row Except inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond action is also unable to reach the hydrogen bond crosslinks of gel point or more；But it is inorganic Containing in polymeric system under boric acid estersil key and optional Inorganic Boron oxygen boron key and hydrogen bond action collective effect can reach Cross-linked structure more than gel point.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein dynamic aggregation object In comprising including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, be unable to reach the covalent cross-linking of gel point or more；Row Except inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond action reaches the hydrogen bond crosslinks of gel point or more.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more in valence component of polymer, and Inorganic Boron oxygen boron key is not present； After excluding inorganic boric acid estersil key, hydrogen bond action is below the gel point of hydrogen bond crosslinks.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key and Inorganic Boron oxygen boron key reach the dynamic covalent cross-linking of gel point or more, Inorganic Boron in valence component of polymer Sour estersil key is more than the gel point of dynamic covalent cross-linking；After excluding inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond is made Below the gel point of hydrogen bond crosslinks.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more in valence component of polymer, and Inorganic Boron oxygen boron key is not present； After excluding inorganic boric acid estersil key, hydrogen bond action is also more than the gel point of hydrogen bond crosslinks.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key and Inorganic Boron oxygen boron key reach the dynamic covalent cross-linking of gel point or more, Inorganic Boron in valence component of polymer Sour estersil key is more than the gel point of dynamic covalent cross-linking；After excluding inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond is made With also more than the gel point of hydrogen bond crosslinks.
In another embodiment of the invention, comprising with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group.
In yet another embodiment of the present invention, include with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group；The sum of wherein inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key are below the gel point of dynamic covalent cross-linking.
In yet another embodiment of the present invention, include with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group；Wherein inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more.
In embodiments of the present invention, dynamic polymer systems can include one or more polymer.Work as presence It when cross-linked network, can be made of one or more cross-linked networks, noncrosslinking component of polymer can also be contained simultaneously.When Include that the dynamic is total simultaneously in the cross-linked network structure when dynamic aggregation object is only made of a cross-linked network Valence is crosslinked and supermolecule hydrogen bond crosslinks；When dynamic aggregation object is simultaneously comprising crosslinking and when non-crosslinked ingredient, non-crosslinked ingredient can be with Homogeneous blend/be interspersed in cross-linked network can not also be evenly dispersed in cross-linked network；It can be between multiple non-crosslinked ingredients Uniformly or be incompatibly blended/interspersed.
The present invention also provides a kind of energy-absorbing methods, which is characterized in that it is poly- to provide a kind of dynamic with hydridization bonding structure Object or composition are closed, and carries out energy-absorbing using it as energy-absorbing material, wherein dynamic aggregation object or composition with hydridization bonding structure In comprising with dynamic inorganic boric acid estersil key (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerize be crosslinked or simultaneously Dynamic covalent polymer ingredient made of polymerization and crosslinking, wherein any one B atom are connect with three-O-, connection at least two Any one divalent or the above linker of divalent of a B atoms are (poly-) siloxy group and optional-O-；Wherein at least part institute Hydrogen bond group is carried on the dynamic aggregation object molecule stated, the hydrogen bond group participates in forming hydrogen bond.
In embodiments of the present invention, the inorganic boric acid estersil key by inorganic compounds of boron and containing silicone hydroxyl and/ Or the silicone compounds of silicone hydroxyl presoma react.
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/ester, boric anhydride, halogenation boron etc. that the inorganic compounds of boron, which is selected from,.
Wherein, described (poly-) silicone compounds containing silicone hydroxyl and/or silicone hydroxyl presoma, refer to the end of compound Containing silicone hydroxyl and/or silicone hydroxyl presoma, and the compound that main chain or agent structure are suitable (poly-) siloxane structure of meaning.
In embodiments of the present invention, the hydrogen bond group, which is characterized in that have hydrogen bond simultaneously in a hydrogen bond group Receptor and hydrogen-bond donor；Can also be that part hydrogen bond group contains hydrogen-bond donor, other part hydrogen bond group contains hydrogen bond receptor.
The receptor of heretofore described hydrogen bond group preferably comprises structure at least one shown in the following general formula (1),
Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Selected from arbitrary Suitable atom, group, segment, cluster；Wherein, R is selected from hydrogen atom, substitution atom, substituent group.
The donor of heretofore described hydrogen bond group preferably comprises at least one of structure shown in the following general formula (2),
Structure shown in general formula (1) and (2) can be side group, end group, linear chain structure, the branched chain structure containing side group, It can be cyclic structure etc..Wherein, the cyclic structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, Caged scaffold, nested ring structure etc..In embodiments of the present invention, the side hydrogen bond group preferably contains general formula (1) simultaneously (2) structure shown in.
In embodiments of the present invention, the form of the dynamic aggregation object or composition with hydridization bonding structure can be with It is solution, lotion, cream, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer Swell gel, ionic liquid swell gel), solid foam etc..
In embodiments of the present invention, the dynamic aggregation object or composition with hydridization bonding structure are in preparation process In it is also an option that property be added the other polymers that can be added/use, auxiliary agent, filler is blended be collectively formed dynamic gather Close object or composition.
In embodiments of the present invention, the dynamic aggregation object or component property are adjustable on a large scale, have extensive Using.Specifically, it can be applied to and make damper, padded coaming, acoustic material, deadener, defense of resistance to impact material Material, athletic protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, shellproof glass The products such as glass squeegee, toughness material, shape-memory material, sealing element, toy, force snesor.
Compared with prior art, the invention has the advantages that：
(1) dynamic covalently inorganic boric acid estersil key, oversubscription are combined in dynamic aggregation object hydridization bonding structure of the invention Sub- hydrogen bond and optional Inorganic Boron oxygen boron key, the advantages of making full use of and combine each bonding action, and dynamic covalent bond It is orthogonal each other with hydrogen bond, coordinate supplement.This, which only contains individually a kind of bonding action therein, to accomplish.Based on difference Dynamic, the difference of response and intensity between bonding can obtain the dynamic change of orthogonality/time sequence and respond and answer Fracture/dissociation under power, to obtain the functions such as multiple response, energy absorption, selfreparing, shape memory to the maximum extent.This It is the prior art not providing.
(2) in the present invention dynamic covalent bond in polymer network/polymer backbone chains only with inorganic boric acid estersil key and Optional boron oxygen boron key connection, and the skeletal chain of dynamic aggregation object only (poly-) siloxanes, can give full play to (poly-) silica Low temperature resistant, the flexible advantage of alkane, is conducive to the performance of polymer dynamic；In the side group/side of (poly-) siloxane backbone chain Hydrogen bond group on chain/branch/bifurcated chain, is further conducive to the performance of hydrogen bond dynamic.
(3) structure-rich of dynamic aggregation object, performance are various in the present invention.By adjusting the function in raw material compound Group number, molecular structure, molecular weight and/or in raw material compound introduce with reactive group, promote dynamic group, With the parameters such as functional group and/or adjustment raw material composition, the dynamic aggregation object with different structure can be prepared, to So that dynamic aggregation object is revealed abundant different performance, meets the application demand of different occasions.
(4) dynamic response of dynamic reversible key is strong in dynamic aggregation object, dynamic response mild condition.Compared to existing Other dynamic covalent systems, it is reversible with good thermal stability and high dynamic that the present invention takes full advantage of inorganic boric acid estersil key Property, can without catalyst, without high temperature, illumination or specific pH under conditions of realize dynamic aggregation object synthesis and dynamic reversible Property, while improving preparation efficiency, the limitation of use environment is also reduced, extends the application range of polymer.This Outside, by optionally control other conditions (such as be added auxiliary agent, adjustment reaction temperature), can under appropriate environment, Accelerate or be quenched dynamic covalent chemical balance, be at required state, this is total in existing supramolecular chemistry and dynamic It is more difficult inside valence system to accomplish.
(5) dynamic aggregation object reflects functional characteristic.By adjusting the dynamic component in dynamic aggregation object, can make to gather It closing object and reveals stimulating responsive and dilatancy, polymer can make a response under the environmental stimulis such as external force, temperature, pH, illumination, Change oneself state.The inorganic boric acid estersil key and supermolecule hydrogen bond of dynamic reversible, can be extraneous by changing after fracture Condition re-starts bonding, so that material has the functional characteristics such as plasticity, self-repairability, extends polymer and uses the longevity While life, but also it can be applied to certain special dimensions.
Specific implementation mode
The present invention relates to a kind of dynamic aggregation object or composition with hydridization bonding structure, it is characterized in that：Wherein include with Dynamic made of dynamically inorganic boric acid estersil key (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerize and/or be crosslinked Covalent polymer ingredient, wherein any one B atom are connect with three-O-, connect any one divalent of at least two B atoms Or the above linker of divalent is (poly-) siloxy group and optional-O-；Dynamic covalent polymer point wherein at least described in part Hydrogen bond group is carried on son, the hydrogen bond group participates in forming hydrogen bond.
According to the embodiment of the present invention, the dynamic covalent polymer with inorganic boric acid estersil key (B-O-Si) key and Optional Inorganic Boron oxygen boron key (B-O-B) is that dynamic covalent bond progress polymerized/cross-linked forms.The inorganic boric acid estersil key and Inorganic Boron oxygen boron key, can be in any appropriate position of dynamic aggregation object chain backbone, both can be in main polymer chain skeleton On, it can also be chained in polymer lateral chain and/or branch and/or bifurcated chain backbone and/or crosslinking.The present invention is also not precluded within Contain inorganic boric acid estersil key and/or Inorganic Boron oxygen boron key, but the Inorganic Boron of the present invention in the side group and/or end group of polymer chain Sour estersil key and optional Inorganic Boron oxygen boron key at least generate polymerization.Since boron atom is trivalent structure, suitable raw material Ingredient generates the inorganic boric acid estersil in polymerization process and Inorganic Boron oxygen boron key can be easy to cause and form bifurcated and can be with And then it is crosslinked.The inorganic boric acid estersil key and Inorganic Boron oxygen boron key contained in the dynamic aggregation object once partly or entirely solves From the covalent polymerized/cross-linked system of dynamic in the dynamic aggregation object is degraded；The dynamic covalent bond will be completely dissociated, And when hydrogen bond action also will be completely dissociated, polymeric system is decomposed into following any or several non-crosslinked lists of secondary Member：Monomer, polymer chain segment, polymer cluster unit etc.；Meanwhile it can be by inorganic between dynamic aggregation object and said units Boric acid estersil key, the reversible keying of Inorganic Boron oxygen boron key and hydrogen bond and dissociation are realized and are mutually converted and dynamic reversible.
Term " polymerization " used reaction in the present invention, is propagation process/effect of chain, including reactant by polycondensation plus The process of product of the reaction formations such as poly-, the ring-opening polymerisation synthesis with higher molecular weight.Among these, reactant is typically The monomer of polymerizing power (can spontaneously be polymerize, or can be polymerize in initiator or outside plus under capable of acting on), The compounds such as oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds or two kinds with The product that upper reactant is polymerize is known as copolymer.It should be pointed out that " polymerization " in the present invention, packet The linear growth process of the chain containing reactant molecule includes the branched process of reactant molecule chain, including reactant molecule chain at Ring process also includes the cross-linking process of reactant molecule chain.
Term " crosslinking " used reaction in the present invention generally refers to lead between reactant molecule and/or in reactant molecule It crosses the chemistry of covalent bond and/or hydrogen bond supramolecular chemistry connects to be formed with two dimension, three-dimensional cluster type and/or three-dimensional unlimited netted The process of type product.In cross-linking process, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, and cluster is gradually formed (can be two dimension or three-dimensional), developing deeply be three-dimensional infinite network.Unless stated otherwise, gel is refered in particular in the crosslinking in the present invention Or more (containing, similarly hereinafter) three-dimensional infinite network structure, non-crosslinked includes line style, branched, cyclic annular, two-dimentional cluster and gel point or less Three-dimensional cluster 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, and be not belonging to across The cross-linked network that can constitute an entirety of entire polymer architecture.
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key (is generally not more than 100 DEG C) under typical temperature and (is generally less than 1 day) more difficult be broken in the usual time comprising But it is not limited only to common carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen Key, nitrogen-nitrogen key etc..
" the dynamic covalent bond " in embodiments of the present invention refers to the inorganic boric acid for participating in polymerized/cross-linked Estersil key and Inorganic Boron oxygen boron key.It should be pointed out that in embodiments of the present invention, Inorganic Boron oxygen boron key is optional dynamic State covalent bond can be adjusted and control according to the selection and recipe ratio of reaction mass.Inorganic Boron oxygen boron key and inorganic boric acid silicon Ester bond is compared, and dynamic is weaker, and for response there is also difference, therefore Inorganic Boron oxygen boron key can be used for adjusting the dynamic of dynamic aggregation object State property.
In embodiments of the present invention, hydrogen bond group is carried at least partly in dynamic covalent polymer molecule, also To be to carry hydrogen bond group on all dynamic covalent polymer molecules or only carried on which part dynamic aggregation object molecule Hydrogen bond group.But any one divalent or the above linker of divalent due at least two B atoms of connection are (poly-) siloxy group With optional-O-, the hydrogen bond group is not connected to or the part as linker participates in connection any two or two or more B Atom.Can be in all or part of suitable of polymer molecule in dynamic covalent polymer molecule with hydrogen bond group The hydrogen bond group is carried on position, the suitable position includes but are not limited to the side of described (poly-) siloxane unit End segment skeleton/side group/side chain of base/side chain, the end group of dynamic covalent polymer molecule, dynamic covalent polymer molecule；Institute State the segment that end segment refers to only one end connection dynamic covalent bond.It is preferred that at least partly Si of (poly-) siloxy group is former Group and/or segment with hydrogen bond group are connected on son.(poly-) siloxane unit being connected with B atoms can be not connected to Group with hydrogen bond group and/or segment.In the present invention, it is preferred to which the Si on the polysiloxane chain being connect with B atoms is former It is connected with group and/or segment with hydrogen bond group on son, is conducive to dynamic covalent bond and hydrogen bond plays quadrature-synergy effect. The hydrogen bond group participates in forming hydrogen bond action.Situations such as according to the quantity of hydrogen bond group, structure and distribution, hydrogen bond action can be with It is polymerization, cyclization, interchain linkage in chain.In the present invention, hydrogen bond action can be by same compound/polymer Hydrogen bond group is realized, can also be realized by the hydrogen bond group in compound/polymer not of the same race.
In the present invention, described (poly-) siloxy group, main chain or agent structure 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 connect group/segment on the silicon atoms, be each independently selected from H, halogen atom and it is any other it is suitable it is organic, Inorganic group/segment, including hydroxyl and other reactive organic groups；Preferably organic group/segment, more preferably contains Carbon organic group/segment；Preferably at least part R1And/or R2For group and/or segment with hydrogen bond group.(poly-) Siloxy group linker can have any appropriate topological structure, and including but not limited to line style, ring-type (include but not limited to single Ring, polycyclic, bridged ring, nested rings), it is branched (include but not limited to combed, H-type, star-like, dendritic, hyperbranched type), two dimension/tri- Tie up cluster, even crosslinked particle, and combinations thereof form.
It in embodiments of the present invention, can be with other than the covalent ingredient of dynamic that B-O-Si keys and B-O-B keys are formed Including other compositions such as other polymers, small molecule, fillers, wherein hydrogen bond group can also be carried.
Any cross-linked network is dynamic crosslinking network in the present invention, including dynamic covalent cross-linking and/or supermolecule hydrogen Key is crosslinked；Once dynamic crosslinking effect dissociation, cross-linked structure just dissociate.But it is not excluded in the composition of the dynamic aggregation object The particle (including fiber and sheet-like particle) of common covalent cross-linking containing filling.
In an embodiment of the invention, dynamic aggregation object or group become non-crosslinking structure, wherein in inorganic boric acid Also the cross-linked structure of gel point or more is not up under estersil key, optional Inorganic Boron oxygen boron key and hydrogen bond collective effect.Wherein Including including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, all dynamic covalent bonds are not enough to form gel point or more Dynamic covalent cross-linking；And hydrogen bond action is also not enough to form the hydrogen bond crosslinks of gel point or more；Dynamic covalent bond and hydrogen bond are made With the sum of be also not enough to form the cross-linked structure of gel point or more.That is, in the present embodiment, even if all dynamics are covalent Key and hydrogen bond are in generation state, and polymeric system remains as non-crosslinking structure, have the corresponding rheological characteristic of non-crosslinking structure Energy.In the present invention, the topological structure of noncrosslinking dynamic covalent polymer can have line style, ring-type (including but not limited to Monocycle, polycyclic, bridged ring, nested rings), it is branched (include but not limited to combed, H-type, star-like, dendritic, over-expense Change type), cluster and combinations of the above form.Polymer chain have side group, side chain, bifurcated chain, branch, and side group, side chain, Bifurcated chain, branch can continue, with side group, side chain, bifurcated chain, branch, can also have multilevel hierarchy.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Include to be unable to reach the covalent of gel point or more including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key in valence polymer Crosslinking；Inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key are excluded, hydrogen bond action is also unable to reach the hydrogen of gel point or more Key is crosslinked；But under inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key and hydrogen bond action collective effect in polymeric system Contain the cross-linked structure that can reach gel point or more.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Include to be unable to reach gel point or more including inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key in valence component of polymer Covalent cross-linking；Inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key are excluded, hydrogen bond action reaches the hydrogen bond of gel point or more Crosslinking.Once hydrogen bond will be completely dissociated, polymeric system will be unable to form cross-linked structure.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more in valence component of polymer, and Inorganic Boron oxygen boron key is not present； After excluding inorganic boric acid estersil key, hydrogen bond action is below the gel point of hydrogen bond crosslinks.Once dynamic covalent bond will be completely dissociated, gather Objects system is closed to will be unable to form cross-linked structure.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key and Inorganic Boron oxygen boron key reach the dynamic covalent cross-linking of gel point or more, Inorganic Boron in valence component of polymer Sour estersil key is more than the gel point of dynamic covalent cross-linking；After excluding inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond is made Below the gel point of hydrogen bond crosslinks.Once dynamic covalent bond will be completely dissociated, polymeric system will be unable to form cross-linked structure.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more in valence component of polymer, and Inorganic Boron oxygen boron key is not present； After excluding inorganic boric acid estersil key, hydrogen bond action is also more than the gel point of hydrogen bond crosslinks.Even if in dynamic covalent bond and hydrogen bond One kind will be completely dissociated, polymeric system still can keep dynamic crosslinking structure.
In yet another embodiment of the present invention, dynamic aggregation object or group become cross-linked structure, wherein the dynamic is total Inorganic boric acid estersil key and Inorganic Boron oxygen boron key reach the dynamic covalent cross-linking of gel point or more, Inorganic Boron in valence component of polymer Sour estersil key is more than the gel point of dynamic covalent cross-linking；After excluding inorganic boric acid estersil key and Inorganic Boron oxygen boron key, hydrogen bond is made With also more than the gel point of hydrogen bond crosslinks.Even if one kind in dynamic covalent bond and hydrogen bond will be completely dissociated, polymeric system is still Dynamic crosslinking structure can so be kept.
In another embodiment of the invention, comprising with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group.
In yet another embodiment of the present invention, include with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group；The sum of wherein inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key are below the gel point of dynamic covalent cross-linking.
In yet another embodiment of the present invention, include with the inorganic boric acid estersil key of dynamic in dynamic aggregation object or composition (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization and/or crosslinking made of dynamic covalent polymer ingredient, wherein Any one B atom is connect with three-O-, any one divalent or the above linker of divalent for connecting at least two B atoms are (poly-) siloxy group and optional-O-；Hydrogen bond base is carried in the side group and/or side chain of at least partly described (poly-) siloxy group Group；Wherein inorganic boric acid estersil key reaches the dynamic covalent cross-linking of gel point or more.
In embodiments of the present invention, dynamic aggregation object or compositional system can include one or more polymer. It when there are cross-linked network, can be made of one or more cross-linked networks, noncrosslinking polymer can also be contained simultaneously Ingredient.Include described simultaneously in the cross-linked network structure when dynamic aggregation object is only made of a cross-linked network Dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks；It, can be with when dynamic aggregation object is made of two or more cross-linked networks It is made of, can also be made of two or more mutually interspersed cross-linked networks two or more cross-linked networks being mutually blended, It cross-linked network that is mutually interspersed and/or being blended can also be made of two or more parts, but the present invention is not limited only to this；Its In, two or more cross-linked networks may be the same or different, and it only includes partly supermolecule hydrogen bond crosslinks that can be, or Be in each cross-linked network all and meanwhile include dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks combination.When dynamic aggregation object is same When comprising crosslinking and when non-crosslinked ingredient, non-crosslinked ingredient can be with homogeneous blend/be interspersed in cross-linked network, can not also be uniform Ground is dispersed in cross-linked network；It can uniformly or incompatibly be blended/intert between multiple non-crosslinked ingredients.When polymer is non- When crosslinking, partial polymer can only have hydrogen bond, and part or all of polymer can contain dynamic covalent bond and hydrogen bond simultaneously.
For the dynamic aggregation object of the present invention, when dynamic covalent cross-linking reaches dynamic altogether at least one cross-linked network When more than valence crosslinked gel point, it is ensured that even if only there are one in the case of cross-linked network, even if all described super When molecule hydrogen bond dissociates, polymer can also have cross-linked structure under given conditions.When there are two or more cross-linked networks When, can there are interaction (including the covalent boric acid estersil key of the dynamic and/or supermolecule hydrogen bond between different cross-linked networks Effect), it can also be mutual indepedent.Due to inorganic boric acid estersil key and Inorganic Boron oxygen boron key in dynamic, response, intensity just There are difference, the two is had any different with hydrogen bond in terms of dynamic, response and intensity again, therefore passes through dynamic covalent bond and hydrogen The Combination Design of key can regulate and control polymer architecture and obtain ideal and various performance.By the difference of dynamic, can produce The dynamic behaviour of raw sequence；By the difference of response, orthogonal and/or collaboration and/or the response of secondary sequence can be generated；Base In the difference of intensity, multi-level external force dissociation can be generated.
Based on the dynamic of the dynamic covalent bond and hydrogen bond, polymer of the invention can show stress/strain sound Ying Xing, especially dilatant performance.When the dynamic aggregation object is non-crosslinking structure, even if will still if system generation dilatant Without generating elastic state be conducive to that mechanical energy is lost by VISCOUS FLOW completely for viscous state.When the dynamic aggregation object For dynamic crosslinking structure when, system when dilatant occurs, will occur cohesive elastomeric conversion or elasticity enhancing, with viscosity damage The material damage under stress is avoided or reduced while consumption again.Two kinds of situations respectively have feature and advantage.
In embodiments of the present invention, it can be blended and/or be interspersed with one in the cross-linked network structure of dynamic aggregation object Kind or it is a variety of do not have the key containing B-O-Si and the dynamic aggregation object of optional B-O-B keys between interaction other polymerize Object.In the present invention, it (includes but not limited to monocycle, more that the topological structure of the other polymers, which can have line style, ring-type, Ring, bridged ring, nested rings), it is branched (include but not limited to combed, H-type, star-like, dendritic, hyperbranched type), The even crosslinked particle of cluster and combinations of the above form.Polymer chain has side group, side chain, bifurcated chain, branch, and Side group, side chain, bifurcated chain, branch can continue, with side group, side chain, bifurcated chain, branch, can also have multilevel hierarchy.
It is also possible to there is other diversified hydridization embodiments, those skilled in the art can root According to the logic and train of thought of the present invention, rationally and effectively realize.
The present invention also provides a kind of energy-absorbing methods, which is characterized in that it is poly- to provide a kind of dynamic with hydridization bonding structure Object or composition are closed, and carries out energy-absorbing using it as energy-absorbing material, wherein dynamic aggregation object or composition with hydridization bonding structure In comprising with dynamic inorganic boric acid estersil key (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerize be crosslinked or simultaneously Dynamic covalent polymer ingredient made of polymerization and crosslinking, wherein any one B atom are connect with three-O-, connection at least two Any one divalent or the above linker of divalent of a B atoms are (poly-) siloxy group and optional-O-；Wherein at least part institute Hydrogen bond group is carried on the dynamic aggregation object molecule stated, the hydrogen bond group participates in forming hydrogen bond.
In embodiments of the present invention, the inorganic boric acid estersil key can be by inorganic compounds of boron and containing silicone hydroxyl And/or the silicone compounds of silicone hydroxyl presoma react.
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：
Described (poly-) silicone compounds containing silicone hydroxyl and/or silicone hydroxyl presoma contain in the structure for referring to compound There are silicone hydroxyl and/or a silicone hydroxyl presoma, and main chain or compound that agent structure is any appropriate (poly-) siloxane structure. The main chain or agent structure of (poly-) siloxanes 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；It is excellent Select at least partly R1And/or R2For group and/or segment with hydrogen bond group.Other described reactive organic groups are only used for Graft modification is carried out to (poly-) siloxanes, such as obtains hydrogen bond group, change hydrophilic and hydrophobic, connection fluorophor etc., and do not have to In group/segment of the connection containing inorganic boric acid estersil key.Described (poly-) siloxanes containing silicone hydroxyl and/or silicone hydroxyl presoma Compound is selected from small molecule silicone compounds and macromolecular polysiloxane compound, 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 Shape (include but not limited to monocycle, polycyclic, bridged ring, nested rings), it is branched (include but not limited to combed, H-type, star-like, dendritic, Hyperbranched type), two-dimensional/three-dimensional cluster, even crosslinked particle, and combinations thereof form.It can be in one dynamic aggregation object It must satisfy there are many (poly-) siloxanes of (poly-) siloxanes, but the present invention and carry hydrogen on at least partly described dynamic aggregation object Key group.
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.
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 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：
In the present invention, any appropriate inorganic compounds of boron may be used and silicone compounds combination is inorganic to be formed Boric acid estersil key, it is preferred to use inorganic boric acid and organopolysiloxane, inorganic boric acid and siliceous hydroxyl groups precursors containing silicone hydroxyl Organopolysiloxane, inorganic borate (salt) and the organopolysiloxane containing silicone hydroxyl form boric acid estersil key, more preferably It is formed with the organopolysiloxane containing silicone hydroxyl using inorganic boric acid and organopolysiloxane, inorganic borate containing silicone hydroxyl Boric acid estersil key more preferably forms boric acid estersil key using inorganic borate and the organopolysiloxane containing silicone hydroxyl.
In embodiments of the present invention, any appropriate mode may be used and form Inorganic Boron oxygen boron key, it is preferably inorganic It is formed with inorganic borate dealcoholysis using boric acid dehydration, inorganic boric acid.
In embodiments of the present invention, except the silicon atom on (poly-) siloxy group being preferably connected with boron atom It can be connected with outside the hydrogen bond group, contain hydrogen bond base in other compounds that can also contain in polymeric system Group, including but not limited to other carbochain polymers, carbon heterochain polymer, element polymer, preferably siloxanes, to improve phase Capacitive.It can be connected on the silicon atom of (poly-) siloxy group/compound by any appropriate chemical reaction mode described Hydrogen bond group, before or after forming the inorganic boric acid estersil key or the hydrogen bond group can be formed simultaneously.
In embodiments of the present invention, the number of teeth that hydrogen bond is formed to the hydrogen bond group does not limit.If hydrogen bond The number of teeth is more, then intensity is big, then the dynamic of hydrogen bond crosslinks with regard to weak, can play promote dynamic aggregation object keep balanced structure and Improve the effect of mechanical property (modulus and intensity).If the number of teeth of hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond crosslinks is just By force, dynamic property, such as self-repairability, energy absorption characteristics can be preferably provided.In embodiments of the present invention, preferably do not surpass Cross the hydrogen bond crosslinks of four teeth.
The number of teeth is donor (D, that is, hydrogen atom) and the receptor (A, that is, receive hydrogen atom by hydrogen bond group Electronegative atom) constitute hydrogen bond quantity, each D-A be combined as a tooth (be shown below, list respectively a tooth, two teeth and The hydrogen bond bonding situation of three tooth hydrogen bond groups).
In embodiments of the present invention, the hydrogen bond group can be any appropriate hydrogen bond group.It is preferred that a hydrogen There are hydrogen bond receptor and hydrogen-bond donor simultaneously in key group；Can also be that part hydrogen bond group contains hydrogen-bond donor, other part hydrogen Key group contains hydrogen bond receptor；Most preferably contain receptor and donor simultaneously.
The receptor of heretofore described hydrogen bond group preferably comprises at least one of structure shown in the following general formula (1),
Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Selected from arbitrary Suitable atom, group, segment, cluster；Wherein, R is selected from hydrogen atom, substitution atom, substituent group.
When as substituent group, the carbon atom number of R is not particularly limited, preferably carbon atom number be 1~20, more preferably 1~ 10。
When as substituent group, the structure of R is not particularly limited, including but not limited to linear chain structure, the branch link containing side group Structure or cyclic structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, excellent Select aliphatic ring.
When as substituent group, R can contain hetero atom, can not also contain hetero atom.
R can be selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substituted miscellaneous hydrocarbon Base.Wherein, the substitution atom in R or substituent group are not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing heteroatomic It is any in substituent group.
R is more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20It is fat miscellaneous alkyl, miscellaneous Aryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20It is any in alkyl sulfenyl acyl group, artyl sulfo acyl group The substituted form of kind atom or group or any group.
Specifically, R can be selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, ethyl, n-propyl, different Propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, Pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, acrylic, vinyl, benzene Base, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto Carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzylaminocarbonyl, methoxyl group thiocarbonyl, second Oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, ethylmercapto group thiocarbonyl, benzene sulphur Base thiocarbonyl, benzylthio thiocarbonyl, ethylamino thiocarbonyl, benzyl aminothiocarbonyl, substituted C1-20Alkyl, substitution C1-20Alkenyl, substituted aryl, substituted aryl, substituted C1-20Fat miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl hydrocarbon Base, substituted C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, substituted aryl sulphur The C of base carbonyl substitution1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl alkylthio carbonyl Any atom or group in base, substituted artyl sulfo thiocarbonyl etc..Wherein, butyl includes but not limited to normal-butyl, uncle Butyl.Octyl includes but not limited to n-octyl, 2- ethylhexyls.Wherein, atom or substituent group is replaced to be selected from halogen atom, alkyl Substituent group, containing any in heteroatomic substituent group.
The donor of heretofore described hydrogen bond group preferably comprises at least one of structure shown in the following general formula (2),
Structure shown in general formula (1) and (2) can be side group, end group, linear chain structure, the branched chain structure containing side group, It can be cyclic structure etc..Wherein, the cyclic structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, Caged scaffold, nested ring structure etc..
In embodiments of the present invention, the hydrogen bond group preferably contains structure shown in general formula (1) and (2) simultaneously.Root According to the implementation result of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, thiocarbamate base, urea groups, pyrrole Azoles, imidazoles, imidazoline, triazole, purine, porphyrin and their derivative.
In embodiments of the present invention, it is connected on the silicon atom of preferably described (poly-) siloxy group/compound described Hydrogen bond group simultaneously contain hydrogen bond donor and receptor, can directly to form hydrogen bond action in-between, without other Ingredient simplifies polymer composition and preparation process.
As an example, the end group hydrogen bond group on the side group hydrogen bond group and end group in side group can be enumerated as follows Structure, but the present invention is not limited only to this.
Wherein m, n are the quantity of repetitive unit, can be fixed values, can also be average value, preferably shorter than 20, more preferably Less than 5.In the present invention, it can contain in same polymer and have more than a kind of above-mentioned side hydrogen bond group, in the same network It can also contain and have more than a kind of above-mentioned side hydrogen bond group.Compound to that can import the side hydrogen bond group has no special limit It is fixed, it is correspondingly formed reaction type and mode of the group etc. and is also not particularly limited.Such as：Pass through carboxyl, acyl halide group, acid anhydrides Covalent reaction between group, ester group, amide groups, isocyanate groups and amino is formed；By isocyanate groups and hydroxyl, Covalent reaction between sulfydryl, carboxyl is formed；Pass through the covalent reaction between succinimide group and amino, hydroxyl, sulfydryl It is formed.
Preferably the skeleton hydrogen bond group on Suitable polymer components main chain and/side chain/branch/bifurcated chain backbone is lifted Such as (but the present invention is not limited only to this)：
In embodiments of the present invention, can by formed inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key come The dynamic aggregation object is generated, can also first be prepared containing the inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key Compound again polymerized/cross-linked to generate the dynamic aggregation object.
In embodiments of the present invention, the form of the dynamic aggregation object or composition with hydridization bonding structure can be with It is solution, lotion, cream, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer Swell gel, ionic liquid swell gel), foam etc., wherein the dissolvable small molecule contained in ordinary solid and solid foam Amount component content is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Its In, the shape and volume of dynamic aggregation object ordinary solid are relatively more fixed, and intensity is high, and density is big, suitable for the explosion-proof of high intensity Wall or apparatus housings；Elastomer has the general properties of ordinary solid, but elasticity is more preferable, pliability higher, is more suitable for making For energy-absorbing materials such as damping/dampings；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 in the general foamed plastics such as low with density, light, specific strength is high When advantage, soft foam material also has good elasticity and energy absorption capacity.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention is not limited only to this, and 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 hydridization bonding structure Dynamic aggregation composition formula component, or play the role of in the preparation process of dynamic aggregation object improving processing performance.
The other polymers added/used can play improvement material as additive in system Material new capability can, be assigned, materials'use and economic benefit is improved, has the function that material comprehensively utilizes.It can add/use Other polymers can be selected from natural polymer, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to being added Polymer character and possessed molecular weight do not limit, can be oligomer, Huo Zhegao according to the difference of molecular weight Polymers can be homopolymer or copolymer according to the difference of polymeric species, in the specific use process should be according to target material The performance of material and the needs of actual fabrication process and selected.
When the other polymers that can be added/use be selected from natural polymer when, can be selected from it is following any or Appoint several natural polymers：Natural rubber, chitosan, chitin, native protein etc..
When the other polymers that can be added/use are selected from synthetic resin, it can be selected from following any or appoint several conjunctions At resin：Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), Medium density polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, Polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- carbon Acid esters, dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane are total Polymers, polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, highly resistance Rush polystyrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetate Vinyl ester copolymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride- Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP) etc..
When the other polymers that can be added/use are selected from synthetic rubber, it can be selected from following any or appoint several conjunctions At rubber：Isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, Fluorubber, lactoprene, polysulfide rubber, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc..
When the other polymers that can be added/use are selected from synthetic fibers, it can be selected from following any or appoint several conjunctions At fiber：Viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane are fine Dimension, polyacrylonitrile fibre, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..
In the preparation process of polymer material, the preferred natural rubber of other polymers that can add/use, polyethylene, Polypropylene, vinyl-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, Epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, second third Rubber, silicon rubber, polyurethane rubber, thermoplastic elastomer (TPE).
The auxiliary agent for adding/using, can improve material preparation process, improve product quality and yield, drop Low product cost assigns product certain distinctive application performance.The auxiliary agent for adding/using is selected from following any Kind appoints several auxiliary agents：Additive synthesis, including catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat are steady Determine agent；Improve the auxiliary agent of mechanical property, including chain extender, toughener, coupling agent；Improve the auxiliary agent of processing performance, including lubrication Agent, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent.
Catalyst in the auxiliary agent can reduce reaction activity to accelerate to react by changing reaction path The reaction rate of object during the reaction.In embodiments of the present invention, the catalyst includes but are not limited to：(1) Polyurethane catalyst for synthesizing：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (diformazan ammonia Base propyl) diisopropanolamine (DIPA), N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- bis- Methyl cyclohexylamine, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- bis- Methylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls caproic acid, N, N- diformazans Base benzylamine, N, N- dimethyl cetylamines etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, two pungent Base tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, acetic acid benzene Mercury, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc..(2) polyolefin catalyst for synthesizing：Such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, four chlorinations Titanium, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, three oxidations Two antimony, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc..(3) CuAAC reacts Concerted catalysis is shared by monovalence copper compound and amine ligand.Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3 Deng；It can also be by elemental copper and cupric compound (such as CuSO4、Cu(OAc)2) in-situ preparation during the reaction；Wherein, Cu (I) the preferred CuBr (PPh of salt preferred CuBr and CuI, Cu (I) complex compound3)3.Amine ligand can be selected from three [(1- benzyls -1H-1,2,3- Triazole-4-yl) methyl] amine (TBTA), three [(1- tertiary butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzene And imidazolmethyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；Wherein, amine ligand preferred TBTA and TTTA.(4) Thiol-ene catalysts：Photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyls phenylacetone, 2,2- dimethoxies Base -2- phenyl acetophenones etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethylamino pyrroles Pyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01-2wt%.
Initiator in the auxiliary agent for adding/using, can cause monomer molecule in polymerization process It activates and generates free radical, improve reaction rate, reaction is promoted to carry out, include but are not limited to following any or appoint several draw Send out agent：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, peroxide Change bis- (4- tert-butylcyclohexyls) esters of two dicyclohexyl carbonates, dicetyl peroxydicarbonate, tert butyl peroxy benzoate, tertiary butyl Peroxidating pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred peroxidating of initiator Lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1-1wt%.
Antioxidant in the auxiliary agent for adding/using can delay the oxidation process of polymer samples, ensure Material can be carried out successfully preparing processing and extend its service life, included but are not limited to following any or appointed several anti- Oxygen agent：Hinered phenols, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyls Base phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl- 6- tert-butyl phenols]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros are equal Triazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent for adding/using can prevent polymer samples from light aging occurs, and extend Its service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide Titanium, zinc oxide, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxies two Benzophenone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzo three Azoles, 2,4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethyls Own ester；Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as Bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl esters), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light Stabilizer, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2, 2,6,6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- bis- uncles Butyl benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, N '-di-n-butyl dithiocarbamates Nickel formate etc.；Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent for adding/using enables to polymer samples processing or using Chemical change does not occur because heated in journey, or delays these variations to achieve the purpose that prolong the service life comprising but It is not limited only to following any or appoints several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, disalt Base lead stearate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, two Alkali lead phthalate, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, hard Resin acid calcium, lead stearate, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, tin dilaurate di-n-octyl Tin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital Tin C-102, dimercapto acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptans type Salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxyfatty acid Ester, epoxy resin；Phosphorous acid esters, as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, Aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Wherein, The preferred barium stearate of heat stabilizer, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat used Stabilizing agent dosage is not particularly limited, generally 0.1-0.5wt%.
Chain extender in the auxiliary agent for adding/using, can be with the reaction-ity group reaction on reactant molecule chain And make strand extension, molecular weight increase, be commonly used for preparing addible polyurethane/polyurea comprising but be not limited only to Under it is any or appoint several chain extenders：Polyalcohols chain extender, such as ethylene glycol, propylene glycol, diglycol, glycerine, three hydroxyls Methylpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, hydroquinone two hydroxy ethyl ether (HQEE), the double hydroxyls of resorcinol Ethylether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, as diaminotoluene, diamino dimethylbenzene, tetramethyl are sub- Xylylene diamine, tetraethyl diphenyl methylene diamines, tetra isopropyl hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminos Methyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiands (MOCA), 3,5- dimethyl sulphur-based first Phenylenediamine (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1,3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcohol Amine chain extender, such as triethanolamine, triisopropanolamine, N, bis- (2- hydroxypropyls) aniline of N '-.Chain extender dosage used is without spy It does not limit, generally 1-20wt%.
Toughener in the auxiliary agent for adding/using can reduce polymer samples brittleness, increase toughness, carry High material bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-fourth two Alkene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, propylene Nitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, benzene Ethylene-butadiene-styrene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene (ABS) copolymerization Object (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), methyl methacrylate-butadiene-styrene copolymerization Resin (MBS), chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent for adding/using, can improve polymer samples and inorganic filler or increasing The interface performance of strong material, reduces the viscosity of material melt in plastic processes, improves the dispersion degree of filler and is added with improving Work performance, and then product is made to obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any Kind appoints several coupling agents：Chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, Aluminate Coupling agent etc.；Wherein, the preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(2,3- epoxies third Oxygen) propyl trimethoxy silicane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5- 2wt%.
Lubricant in the auxiliary agent for adding/using can improve the lubricity of polymer samples, reduce and rub It wipes, reduce Interface Adhesion performance comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbons Class, such as solid paraffin, microcrystalline wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, it is such as stearic Acid, hydroxy stearic acid；Fatty acid ester, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax； Aliphatic amide type, such as stearmide or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylenes are double stearic Amide；Fatty alcohol and polyalcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, Barium stearate, magnesium stearate, zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight Polyethylene.Lubricant quantity used is not particularly limited, generally 0.5-1wt%.
Releasing agent in the auxiliary agent for adding/using, it can make polymer samples be easy to demould, surface is smooth, It is clean comprising but be not limited only to following any or appoint several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon Oil, methyl phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon Rubber etc.；Wherein, the preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5-2wt%.
Plasticizer in the auxiliary agent for adding/using, can increase the plasticity of polymer samples so that polymerization Hardness, modulus, softening temperature and the brittle temperature of object decline, and elongation, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fat Fat esters of gallic acid, such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite Esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyls) oneself Ester, epoxy soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box acetylated castor oil Sour methyl esters；Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester, phenyl alkylsulfonate, Trimellitate, citrate and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), adjacent benzene Dibutyl carboxylic acid (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), O-phthalic Sour diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Foaming agent in the auxiliary agent for adding/using can make polymer samples foaming pore-forming, to obtain matter Gently, heat-insulated, sound insulation, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.
Dynamic regulation agent in the auxiliary agent for adding/using can be promoted and adjust dynamic aggregation object dynamic, with Just the expected performance of optimization is obtained, is usually that either free carboxyl group or can provide or receive electricity with free hydroxyl The compound of son pair, includes but are not limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc.. Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt%.
Antistatic agent in the auxiliary agent for adding/using can draw the deleterious charge assembled in polymer samples It leads or eliminates, make it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several Antistatic agent：Anionic antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethyl Alcohol amine salt, to nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkane Base dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, N- lauryls- Bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol epoxy It is ethane additive product, fatty acid ethylene oxide addition product, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, sweet Oily mono fatty acid ester；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyene propionamide N- seasons such as ethylenediamine Ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, the preferred lauryl of antistatic agent Trimethyl ammonium chloride, octadecyldimethyl ethoxy quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used is not particularly limited, generally 0.3-3wt%.
Emulsifier in the auxiliary agent for adding/using can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitutes the surface tension between phase, is allowed to form uniform and stable dispersion or emulsion, is preferred for carrying out lotion Polymerized/cross-linked comprising but be not limited only to following any or appoint several emulsifiers：Anionic, such as higher fatty acid salt, alkane Base sulfonate, alkylbenzene sulfonate, Negel, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor Sesame oil sulfuric acid, sulphation butyl ricinoleate salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, as alkylammonium salt, Alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic Type, as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide add At object, fatty acid glyceride, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, alcohol Amine fatty acid amide etc.；Wherein, the preferred neopelex of emulsifier, sorbitan fatty acid ester, triethanolamine are stearic Acid esters (Emulphor FM).Emulsifier used is not particularly limited, generally 1-5wt%.
Dispersant in the auxiliary agent for adding/using enables to solid flocculation group point in mixed with polymers liquid It dissipates and is suspended in liquid for tiny particle, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, simultaneously Also it can prevent the sedimentation and cohesion of particle, be formed and stabilize suspension comprising but be not limited only to following any or appoint several points Powder：Anionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as fat Fat alcohol polyoxyethylene ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Wherein, divide The preferred neopelex of powder, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.Point used Powder dosage is not particularly limited, generally 0.3-0.8wt%.
Colorant in the auxiliary agent for adding/using, can make polymeric articles show required color, Increase surface color and polish comprising but be not limited only to following any or appoint several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium Red, iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalein Cyanines are red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, intellectual circle Blue RSN, slag rhodamine toner, Oil Yellow etc.；Wherein, the selection of colorant, need not be special depending on color sample demand It limits.Colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent for adding/using can make contaminated substance obtain the glittering of similar fluorite Luminous effect comprising but be not limited only to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, Pyrazoline type, benzo oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent Bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of (fluorescent brightener CBS), 4,4-, 2,2- (4,4 ' - Diphenylethyllene) dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002-0.03wt%.
Delustering agent in the auxiliary agent for adding/using when incident light being enabled to reach polymer surfaces, occurs Diffusing reflection generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents：It is heavy Barium sulfate, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc. drop；Wherein, the preferred dioxy of delustering agent SiClx.Delustering agent dosage used is not particularly limited, generally 2-5wt%.
Fire retardant in the auxiliary agent for adding/using, can increase the flame resistance of material comprising but not only limit In following any or several fire retardants：Phosphorus system, as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, Phosphate toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Have Machine halide, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；It is inorganic fire-retarded Agent, such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos Propyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, and one As be 1-20wt%.
Nucleating agent in the auxiliary agent for adding/using can accelerate knot by the crystallization behavior of change polymer Brilliant rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, the raising product transparency, The purpose of the physical mechanical properties such as lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, packet It includes but is not limited only to following any or appoints several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid Sodium, silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, nucleating agent is preferred Silica, benzylidene sorbitol (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
It is good can to ensure that polymer has during film for rheological agent in the auxiliary agent for adding/using Brushability and coating thickness appropriate, prevent storage when solid particle sedimentation, its redispersibility can be improved comprising but It is not limited only to following any or appoints several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, carbonic acid Calcium, lithium chloride, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound is such as hard Resin acid aluminium, aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanic acid Ester derivant, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferably organic swelling of rheological agent Soil, polyethylene wax, hydrophobically modified alkalinity swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used It is not particularly limited, generally 0.1-1wt%.
Thickener in the auxiliary agent for adding/using, can assign the good thixotropy of mixed with polymers liquid and Consistency appropriate, to meet various need such as its stability and application performance during production, storage and use It asks comprising but be not limited only to following any or appoint several thickeners：Lower-molecular substance, such as fatty acid salt, alkyl dimethylamine It is oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, sweet Oily trioleate, coamidopropyl glycine betaine, titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, micro mist Silica, colloidal aluminum, animal protein, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid are total Polymers, polyacrylamide, polyvinyl pyrrolidone, polyethers etc.；Wherein, the preferred hydroxyl coconut oil diethanol amide of thickener, acrylic acid- Methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the auxiliary agent for adding/using can ensure that the flat smooth of polymer coating film is uniform, change Kind film coated surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Poly dimethyl silicon Oxygen alkane, polymethylphenylsiloxane, polyacrylate, organic siliconresin etc.；Wherein, the preferred polydimethylsiloxanes of levelling agent Alkane, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
In the preparation process of dynamic aggregation object, auxiliary agent preferred catalyst, initiator, antioxidant, the light that can add/use Stabilizer, heat stabilizer, chain extender, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.
The filler primarily serves following effect in dynamic aggregation object：1. reducing the shrinking percentage of moulded products, carry Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjusting the viscosity of polymer； 3. meeting different performance requirement, such as raising polymer material impact strength and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The filler, selected from following any or several fillers：Inorganic non-metallic filler, organic is filled out at metal packing Material.
The inorganic non-metallic filler includes but are not limited to following any or appoints several：Calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, carbon nanotube, molybdenum disulfide, slag, flue dust, wood powder and Shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, oil shale powder, expanded perlite Powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass microballoon, foam microspheres, glass powder, cement, glass Fiber, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, crystalline substance Palpus is equal.
The metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, gold etc. and its Powder, nano particle and the fiber of alloy.
The organic filler includes but are not limited to following any or appoints several：Fur, natural rubber, asbestos, worm Glue, chitin, chitosan, protein, raw lacquer, shell powder, silk, artificial silk, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, chitosan, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
It, can be by any appropriate material hybrid mode known in the art by one in the preparation process of dynamic aggregation object Surely the raw material matched prepares dynamic aggregation object by mixing, and can be interval, semicontinuous or continuous processing form mixing； Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic aggregation object.The hybrid mode packet of use Include but be not limited only to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., wherein it is preferred that Solution is stirred, melting is stirred and melting extrusion.Energy in material mixed process provides form It is limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, injection moulding, mould Molded, tape casting, calendering formation, cast molding.
In the preparation process of dynamic aggregation object, can also be added the foregoing description the other polymers added/used, / use auxiliary agent, can add/filler used can be added to collectively constitute dynamic aggregation object compound system, but these additives It is not necessarily all necessary.
The specific method for preparing dynamic aggregation object, the typically shape by raw material to dissolve or disperse are stirred using solution Formula is stirred mixing in the reactor in respective solvent or in common solvent.In general, hybrid reaction temperature controls At 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, time control is mixed in 0.5-12h, preferably 1-4h.It can incite somebody to action The product obtained after mixing is poured into suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0- 48h obtains polymer samples.Reservation solvent can be selected to be made with solution, lotion, paste, glue etc. during this as needed Polymer samples existing for form, or selection remove solvent and solid-state polymerization existing for the forms such as membranaceous, blocky, foam-like are made Object sample.When preparing dynamic aggregation object in this approach, usually also need to optionally be added initiator in a solvent with polymerisation in solution Mode obtain dynamic aggregation object to cause polymerization, or dispersant is added and oil-soluble initiator is configured to suspension to suspend The mode of polymerization or slurry polymerization obtains dynamic aggregation object to cause polymerization, or addition initiator and emulsifier are configured to milkiness Liquid is caused polymerization in a manner of emulsion polymerization and obtains dynamic aggregation object.Used polymerisation in solution, suspension polymerisation, slurry polymerization And the method for emulsion polymerization, it is well known to those skilled in the art and widely used polymerization, it can be according to reality Situation is adjusted, and is no longer developed in details here.
Used solvent, should carry out according to actual conditions such as reactant, product and reaction process in above-mentioned preparation method Selection includes but are not limited to following any solvent or appoints the mixed solvent of several solvents：Deionized water, acetonitrile, acetone, fourth Ketone, benzene,toluene,xylene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, methanol, ethyl alcohol, chloroform, dichloromethane Alkane, 1,2- dichloroethanes, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, acetic acid isopropyl Ester, n-butyl acetate, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, Phosphate buffer solution, borate buffer solution etc.；It is preferred that deionized water, toluene, chloroform, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene Furans, dimethylformamide, phosphate buffer solution.In addition, solvent is also selected from oligomer, plasticizer, ionic liquid；Described Oligomer includes but are not limited to polyethylene glycol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid Body paraffin etc.；The plasticizer can be selected from classification described in the plasticizer in addible auxiliary agent, and which is not described herein again；It is described Ionic liquid be generally made of organic cation and inorganic anion, cation is usually that alkyl quaternary ammonium ion, alkyl quaternary are seen Imidazol ion, the alkyl-substituted pyridinium ions of N- etc. that ion, 1,3- dialkyl group replace；Anion is usually halide ion, four Fluoro boron acid ion, also has CF at hexafluorophosphoricacid acid ions3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、 (CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -Deng.Wherein, dynamic aggregation is prepared using deionized water Object simultaneously selects when being retained, and can obtain hydrogel；Dynamic aggregation object is prepared using organic solvent and selects to be retained When, organogel can be obtained；When preparing dynamic aggregation object using oligomer and selecting to be retained, oligomer can be obtained Swell gel；When preparing dynamic aggregation object using plasticizer and selecting to be retained, plasticizer swell gel can be obtained；Profit When preparing dynamic aggregation object with ionic liquid and selecting to be retained, ionic liquid swell gel can be obtained.
In above-mentioned preparation method, the compound liquid concentration configured is according to the structure of selected reactant, molecular weight, dissolving Depending on degree and required dispersity, it is not particularly limited, preferred a concentration of 0.1~10mol/L of compound liquid, more preferably For 0.1~1mol/L.
It is stirred the specific method for preparing dynamic aggregation object using melting, typically directly stirs raw material in the reactor It is stirred reaction after mixing mixing or heating melting, such mode is generally gas, liquid or lower melting-point solid in raw material In the case of use.In general, the control of hybrid reaction temperature is at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixing is stirred Time control is mixed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, in 0- 150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, polymer samples are obtained.Dynamic aggregation object is prepared in this approach When, it usually also needs to be optionally added into a small amount of initiator to cause in a manner of melt polymerization or gas-phase polymerization polymerization and obtains dynamic Polymer.The method of its used melt polymerization, gas-phase polymerization, is well known to those skilled in the art and is widely used Polymerization, can be adjusted according to actual conditions, no longer be developed in details here.
The specific method of dynamic aggregation object is mixed with using melting extrusion, be typically add the raw material into extruder into Row squeezes out blending reaction, and extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be cut into conjunction after direct tape casting Suitable size either carries out obtained extrusion sample to utilize injection molding machine or moulding press to carry out sample preparation after being crushed.Injection temperature is 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature be 0-280 DEG C, preferably 25-150 DEG C, more It is preferred that 25-80 DEG C, clamp time 0.5-60min, preferably 1-10min, the preferred 4-15MPa of molding pressure.Batten can be placed in In suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, final polymer samples are obtained.
In the preparation process of dynamic aggregation object, mole of selected inorganic compounds of boron and (poly-) silicone compounds Equivalent proportion should be at range appropriate, preferably 0.1~10 range, more preferable 0.3~3 range, more preferable 0.8~1.2 Range.In actual fabrication process, those skilled in the art can be adjusted according to actual needs.
In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The dynamic aggregation physical performance is adjustable on a large scale, has broad application prospects, in military aerospace equipment, function Coating and the fields such as coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material all have important answer With.
By using dilatancy, dynamic possessed by dynamic aggregation object, it is explosion-proof that well recovery, fuel oil can be applied to Etc., it may also be used for prepare speed lockup's device of road and bridge；Also it can be applied to making damping shock absorber, for each The vibration isolation of kind motor vehicles, mechanical equipment, bridge, building, when vibrated, can dissipate polymer material a large amount of energy Amount plays damping, to effectively mitigate vibrations；Also it can be applied to buffer packaging material 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 in external force Effect lower suffered vibrations and impact, include the shock wave etc. of explosion generation；As energy-absorbing material, can also carry out sound insulation, Eliminate the noise etc..Using the bond energy intensity and dynamic sex differernce of dynamic covalent bond and hydrogen bond, also can as shape-memory material into It exercises and uses, when the external force is removed, the deformation that material generates in loading procedure can be restored；Had by dynamic aggregation object Some dynamic reversibilities and rate of stressing dependence, prepare the polymer material of stress sensitive type, and a part can be applied to Prepare have mobility and elasticity conversion magic effect toy and body-building material, can be also used for make 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 with good plasticity and can returning The polymer closure glue that receipts are repaired, which can design, prepares the scratch resistant coatings with self-repair function, to extend making for coating With the service life, realizes and the long-effective corrosion of basis material is protected.Huge answer is shown in the fields such as military project, space flight, electronics, bionical Use potentiality.
It is carried out using inorganic boric acid estersil key and hydrogen bond as key can be sacrificed in use, it can pass through order under external force Property fracture, general hydrogen bond is first broken then inorganic boric acid estersil key fracture, absorbs a large amount of energy and assign polymer material With excellent toughness, it is hereby achieved that the polymer material that toughness is splendid, be widely used in military affairs, space flight, movement, the energy, The fields such as building.
Dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specific implementation Example is present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
By the poly- Methyl Hydrogen Polysiloxane Fluid of methoxy group and a certain amount of Tert-butyl Methacrylate, 2- (2- oxygen -1- imidazoles Alkyl) ethyl methacrylate mixing, the active hydrogen atom (hydrogen being directly connected with Si in poly- Methyl Hydrogen Polysiloxane Fluid in control reaction Atom) molal quantity and Tert-butyl Methacrylate, 2- (2- oxygen -1- imidazolidinyls) ethyl methacrylate in double bond molal quantity Ratio be about 4:3:1, addition reaction occurs using chloroplatinic acid as catalyst, organic poly- silica containing side hydrogen bond group is made Alkane.
The above-mentioned organopolysiloxanes containing side hydrogen bond group of 60g and (the 2- methoxyl groups of 100g tri- are added in three-necked flask Ethyl) borate mixing, it is warming up to 80 DEG C after mixing, the deionized water of 4ml, the nanoclay of 300 mesh of 0.7g is added, Polymerisation is carried out under stirring.During polymerization, the viscosity of silicone oil constantly rises, and after reacting 90min, can be obtained Polymeric liquid with larger viscosity is poured into suitable mold, the 4h that is placed in 80 DEG C of vacuum drying ovens that the reaction was continued, It is cooled to later and is placed at room temperature for 30min, finally obtain soft surface and the transparent polymer sample with larger viscosity.
Surface of polymer material intensity is relatively low, has unformed property, under external force, material is more ductile, and embodies Go out good tensile toughness, can largely be stretched and not broken (elongation at break is more than 2000%).In its table It when defect occurs in face, is placed in 60 DEG C of vacuum drying ovens and heats 4h, defect disappears.In the present embodiment, dynamic aggregation object can be grown Phase keep pellucidity, can using polymer as carry self-healing properties super hot melt adhesive or self-adhesive at room temperature materials'use, It also is used as the medium of speed lockup's device and is used for bridge and road construction.
Embodiment 2
Poly dimethyl-Methyl Hydrogen Polysiloxane Fluid (silicon substrate hydrogen content is low) of methoxy group and a certain amount of allylamine is mixed Close, in control reaction the molal quantity of poly dimethyl-Methyl Hydrogen Polysiloxane Fluid active hydrogen atom (directly be connected with Si hydrogen atom) with The ratio of double bond molal quantity is about 1 in allylamine:1, addition reaction occurs using chloroplatinic acid as catalyst, obtained side group contains more The methyl-silicone oil of amino group, i.e., a kind of poly-organosilicon polyamine.
It is 1 that above-mentioned poly-organosilicon polyamine and 4- fluorophenylisocyanates, which are pressed amino and isocyanates molar ratio,:1 is mixed It closes, using triethylamine as catalyst, reacts in methylene chloride, obtained side group contains ureido groups and trimethoxy silane group Organopolysiloxane.
1.0g distillations are added in the organopolysiloxane that above-mentioned 20g side groups contain ureido groups and trimethoxy silane group Water, 1.2g triethylamines, after being stirred to react 4h, 0.8g polymer foamings microballoon, 1.3g fire retardant TPP, 0.6g antimony oxide, After mixing, 1.67g boric acid front threes are added in 0.8g stearic acid, 0.1g irgasfos 168s, 0.1g antioxidant 1010s, high-speed stirred Ester mixes rapidly, and high-speed stirred 30s, when mixture whitens bubbling, is poured into rapidly in suitable mold, is placed in 70 DEG C Under the conditions of carry out shaping foam for 24 hours so that reactive polymeric is complete, finally can be obtained semi-rigid foaming silicone materials.
The expanded material is made to the bulk sample of 20.0 × 20.0 × 20.0mm sizes, is pressed using universal testing machine Contracting performance test, compression speed 2mm/min, it is 0.76 ± 0.12MPa to measure sample compression intensity.Obtained polysiloxanes bubble Foam material have excellent insulation capacity, also have density is small, specific strength is high, good stability of the dimension, recoverable with And can selfreparing many advantages, such as, the field of thermal insulation such as refrigerator, refrigerator and pipeline can be applied to, also can be used as building heat preservation material Material is used.
Embodiment 3
By the poly dimethyl of methoxy group-phenyl hydrogen-containing siloxane (PHMS, molecular weight 5000) and N- allyls -1H- Imidazoles -1- formamides mix, and poly dimethyl-phenyl hydrogen-containing siloxane active hydrogen atom (is directly connected with Si in control reaction Hydrogen atom) molal quantity and N- allyl -1H- imidazoles -1- formamides in the ratio of double bond molal quantity be about 1:1, with chloroplatinic acid Addition reaction occurs as catalyst, obtained side group contains the organopolysiloxane of hydrogen bond group.
3- dimethyls methoxy silane and boric acid are mixed according to equimolar ratio, be heated to 60 DEG C by stir into After row dissolving, a small amount of water reaction 3h is added, obtains a kind of boronic acid compounds containing boric acid estersil key.
The above-mentioned organopolysiloxane containing side hydrogen bond group and the above-mentioned boronic acid compounds containing boric acid estersil key according to Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, be warming up to 80 DEG C after mixing, be added 4ml deionized water, 1g grain sizes are the talcum powder of 50nm, and polymerisation is carried out under stirring, and one kind is prepared and contains side hydrogen bond group and boron The dynamic aggregation object of sour estersil key.
Obtained polymer samples are in rubber-like, can be stretched on a large scale under slower rate of extension, and creep occurs；But If Rapid stretching, demonstrate flexibility feature, being capable of Fast Restoration after being pressed with finger.This product, which can be used as, has evil spirit The toy of unreal elasticity.
Embodiment 4
Methoxy group Polymethyl methacrylate (molecular weight about 4500) and 2- t-butoxycarbonyl amino ethyl mercaptans are pressed According to double bond and the molar ratio of sulfydryl 1:1 mixing, is added the photoinitiator relative to 2- t-butoxycarbonyl amino ethyl mercaptans 0.2wt% Benzoin dimethylether (DMPA) is placed on ultraviolet radioactive 4h in UV crosslinking instrument after stirring fully, obtains one kind is prepared and contain The organopolysiloxane of side hydrogen bond group.
The above-mentioned organopolysiloxane containing side hydrogen bond group and 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids Ester according to terminal siloxane and borate molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, and the foaming of 4.2g microballoons is added Agent, 2g ammonium polyphosphate, 3g carbon blacks, the conductive black of 1000 mesh of 3g, 2.5g di-iron trioxides, the deionized water of 4ml are quickly stirred Mix 30s after mixing, continuation is stirred to react 4h in nitrogen atmosphere, and one kind is prepared and contains side hydrogen bond group and boric acid silicon The flexible foamed silicone materials of ester bond.
Reactant is poured into suitable mold, is placed in 60 DEG C of vacuum drying ovens that the reaction was continued for 24 hours, is cooled to room later Temperature places 30min, and foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, clamp time 10- 15min, pressure 10MPa press sample surfaces with finger, and sample can be sprung back quickly, show good bullet Property, in addition, sample can also extend in a certain range.In the present embodiment, using possessed by cross-linked polymer sample High tenacity, resilience, anti-flammability, can be made into flame resistant filler material, and software man is made with the fabrics such as skin, cloth cladding in surface Tool.
Embodiment 5
(1) bis- chloro- 1,1,3,3,5,5,7,7,9,9,11,11- of 1,11-, ten dimethyl, six siloxanes and ethoxy ylboronic acid are pressed According to the molar ratio 1 of silicone hydroxyl and borate:1 mixing, is added a small amount of water, after being stirred evenly under the conditions of 50 DEG C, reacts 6h, system It is standby to obtain a kind of dynamic aggregation object containing boric acid estersil key, as the 1st network polymer.
(2) N- allyls -1H- imidazoles -1- formamides and 5- vinyl-2-pyrrolidones in molar ratio 1:2 are sufficiently mixed, It is dissolved in 1- butyl -3- methylimidazole hexafluorophosphates ([C4MIM]PF6) ionic liquid, the AIBN of 5mol% is added as initiation Agent is allowed to fully swell in the 1st network polymer, after stirring is sufficiently mixed, pours into the glass board mould for accompanying silica gel pad In, it is placed on ultraviolet radioactive 10h in UV crosslinking instrument, you can it is poly- to obtain a kind of dynamic containing side hydrogen bond group and boric acid estersil key Close object ionic liquid gel.
Above-mentioned dynamic aggregation object ionic liquid gel is displaced into ionic liquid through deionized water, and is gone every 12h replacements Ionized water is primary, replaces 4 times to get a kind of dynamic aggregation object hydrogel containing side hydrogen bond group and boric acid estersil key.
The modulus of hydrogel prepared by the embodiment is in 13kPa, and strain can reach 16 times, and fracture strength is in 59kPa.It should Hydrogel can be used for the amortizing packaging material of breakables.
Embodiment 6
(1) by the poly dimethyl of methoxy group-phenyl hydrogen-containing siloxane (PHMS, molecular weight 10000) and N- allyls- 2- aminomethyl pyrrolidines mix, and the active hydrogen atom of poly dimethyl-phenyl hydrogen-containing siloxane (is directly connected with Si in control reaction Hydrogen atom) molal quantity and N- allyl -2- aminomethyl pyrrolidines in the ratio of double bond molal quantity be about 1:1, with chloroplatinic acid Addition reaction occurs as catalyst, obtained side group contains the organopolysiloxane of hydrogen bond group.
3- chloropropyls dimethyl methoxy silane and boric acid are mixed according to equimolar ratio, are heated to 60 DEG C and are carried out by stirring After dissolving, a small amount of water reaction 3h is added, obtains a kind of boronic acid compounds containing boric acid estersil key.
Above-mentioned side group is contained into the organopolysiloxane of hydrogen bond group and the above-mentioned boronic acid compounds containing boric acid estersil key Molar ratio according to siloxanes and boric acid is about 1:1 mixing, is added a small amount of water, after being stirred evenly under the conditions of 80 DEG C, reacts 6h, A kind of non-crosslinked dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared.
(2) N- allyls -1H- benzimidazolyl-2 radicals-amine, basudin -2,4 5- butane -2- base -5- propyl- 2- alkenyl -1,3-, 6- triketones are 1 according to molar ratio:1 mixing, and 100g mixtures and the dynamic aggregation object obtained by 100g are taken, add 5mol%'s AIBN is initiator and 5wt% carbon fibers, is heated to 80 DEG C of reaction 8h, and being made a kind of by free radical polymerization contains side hydrogen bond The dynamic aggregation object of group and boric acid estersil key.
The dynamic aggregation object mechanical property：Tensile strength 9.8MPa is broken rate elongation 750%.The product has good tough Property, polymer can be prepared and block glue, selfreparing bonding agent, squeegee.And its mechanical property is strong, excellent shock resistance, A kind of defense of resistance to impact pad use can be prepared.
Embodiment 7
By poly- methyl trifluoro propyl-methylhydrogen silicone (molecular weight 12000) of methoxy group and 6- amino -5- second Alkenyl -2 (1H)-pyrimidone mixing, the active hydrogen atom of poly- methyl trifluoro propyl-methylhydrogen silicone is (straight in control reaction Connect the hydrogen atom being connected with Si) molal quantity and ethyl acrylate, -2 (1H)-pyrimidone of 6- amino -5- vinyl in double bond rub Your ratio of number is about 5:4:1, addition reaction occurs using chloroplatinic acid as catalyst, a kind of side group is made and contains hydrogen bond group Fluorine-containing organopolysiloxane.
3- bromopropyls dimethyl methoxy silane and tripotassium borate are mixed according to equimolar ratio, 60 DEG C is heated to and passes through After stirring is dissolved, a small amount of water reaction 3h is added, obtains a kind of borate compound containing boric acid estersil key.
Above-mentioned side group is contained into the fluorine-containing organopolysiloxane of hydrogen bond group and the above-mentioned borate containing boric acid estersil key Compound is according to SiOCH3Molar ratio with BOK is about 1:1 mixing, is added a small amount of water, after being stirred evenly under the conditions of 80 DEG C, instead 6h is answered, a kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared.
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, scratch-resistant and can be into Row recycling and recycling.
Embodiment 8
(1) the polymethyl-benzene base-methyl vinyl silicone (molecular weight about 8000) and 2- mercaptoimidazoles of methoxy group According to double bond and the molar ratio of sulfydryl 1:1 mixing, is added the photoinitiator benzoin dimethylether (DMPA) of 0.2wt%, stirring is filled After point, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains that a kind of organopolysiloxane containing side hydrogen bond group is prepared.
By above-mentioned side group contain hydrogen bond group organopolysiloxane and isopropanol pinacol borate according to Si-OCH3With The molar ratio 1 of B-OR:1 mixing, is added a small amount of water, after being stirred evenly under the conditions of 60 DEG C, reacts 8h, one kind is prepared and contains The dynamic aggregation object of side hydrogen bond group and boric acid estersil key, as the 1st network polymer.
(2) diallyl aminomethoxy antifebrin, Lu's succinimide mercaptans are according to molar ratio 1:1 mixing, is added to In 120wt% plasticizer epoxidized methyl acetorieinoleates, the 1st network polymer of 85wt%, the styrax of 0.2g are added Double methyl ethers (DMPA) and 0.5g Graphene powders are poured into the glass board mould for accompanying silica gel pad, are placed on after stirring is sufficiently mixed Ultraviolet radioactive 8h in UV crosslinking instrument obtains a kind of epoxidized methyl acetorieinoleate containing hydrogen bond group Yu boric acid estersil key The organogel of swelling.
For the modulus of the organogel of epoxidized methyl acetorieinoleate swelling prepared by the embodiment in 20kPa, strain can To reach 15 times, fracture strength is in 100kPa.This organogel can be used for preparing airborne and air-drop defense of resistance to impact material Material.
Embodiment 9
(1) methoxy group Polymethyl methacrylate (molecular weight about 3000) and 5- mercaptomethyl uracils are according to double The molar ratio 1 of key and sulfydryl:1 mixing is added the photoinitiator benzoin dimethylether (DMPA) of 0.2wt% and is put after stirring fully The ultraviolet radioactive 4h in UV crosslinking instrument obtains that a kind of organopolysiloxane containing side hydrogen bond group is prepared.
The above-mentioned organopolysiloxane containing side hydrogen bond group and 2,6- di-tert-butyl -4- tolyl dibutyl ortho-boric acids Ester is according to Si-OCH3With the molar ratio 1 of B-OR:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, Polymerisation is carried out under stirring, a kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared, and is made For the 1st network polymer.
(2) 4,5- dihydros -2- vinyl -1H- imidazoles and 1- (3- pyrrolidinyls) -2- propylene -1- ketone are according to molar ratio 1:1 Mixing, swells in the 1st network polymer, and the AIBN for adding 5mol% is initiator, 80 DEG C of reaction 8h is heated to, by certainly It is made a kind of containing there are many dynamic aggregation objects of side hydrogen bond group and boric acid estersil key by base polymerization.
The product shows good viscoplasticity, has good isolation vibrations and stress buffer effect, while also table Excellent hydrolytic resistance is revealed.When its surface occurs damaged, by heating can be achieved the healing of breakage to again at Type realizes the selfreparing and recycling of material.
Embodiment 10
Poly dimethyl-Methyl Hydrogen Polysiloxane Fluid of methoxy group and 7- vinyl -2 (1H)-quinokysalines are mixed, control The molal quantity of active hydrogen atom in poly dimethyl containing hydrogen silicone oil (hydrogen atom being directly connected with Si) and methyl acrylate in reaction, The ratio of double bond molal quantity is about 10 in 7- vinyl -2 (1H)-quinokysalines:9:1, occur to add using chloroplatinic acid as catalyst At reaction, obtained side group contains the organopolysiloxane of hydrogen bond group.
Above-mentioned side group is contained into the organopolysiloxane of hydrogen bond group and with diphenyl hydrogen borate ester according to Si-OCH3Group With the molar ratio 1 of B-OR groups:1 mixing, is warming up to 80 DEG C after mixing, the deionized water and 30mg graphenes of 2ml is added, Ultrasonic disperse is swollen in the 1st network, and polymerisation is carried out under stirring, and one kind is prepared and contains side hydrogen bond group With the dynamic aggregation object of boric acid estersil key.
The polymer samples can be used as electronic package material or adhesive uses, and during use, can be carried out to it It recycles and reuses, polymer samples have longer service life；Additionally since its conductivity can be sent out with pressure or pulling force Raw sensitive response, is suitable as force snesor.
Embodiment 11
(1) by the poly dimethyl of methoxy group-phenyl hydrogen-containing siloxane (PHMS, molecular weight 6000) and N- (2,2- bis- Ethoxyethyl group)-N'-2- propylene -1- bases-urea mixing, the reactive hydrogen of poly dimethyl-phenyl hydrogen-containing siloxane is former in control reaction It is double in the molal quantity and N- (2,2- diethoxies ethyl)-N'-2- propylene -1- bases-urea of son (hydrogen atom being directly connected with Si) The ratio of key molal quantity is about 1:1, addition reaction occurs using chloroplatinic acid as catalyst, obtained side group contains having for hydrogen bond group Machine polysiloxanes.
The above-mentioned organopolysiloxane containing side hydrogen bond group and three (4- chlorphenyls) borates are according to Si-OCH3Group and The molar ratio 1 of B-OR groups:1 mixing, be warming up to 80 DEG C after mixing, the deionized water of 4ml be added, under stirring into A kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared, as the 1st network polymerization in row polymerisation Object.
(2) limonene oxide extracted from orange peel, and 100psi carbon dioxide, under the catalytic action of beta-diimine zinc Polymerisation occurs, obtains makrolon PLimC.
By above-mentioned makrolon PLimC and 2- aminoothyl mercaptans, 2- t-butoxycarbonyl aminos ethyl mercaptan according to double bond group It is 10 with sulfydryl ratio:5:5 mixing, are added the polymer foaming microballoon of AIBN, 4wt% of 0.3wt% and the 1st net of 80wt% Network polymer quickly stirs to bubble is generated through professional equipment, is then injected into mold rapidly, cures 30min at room temperature, Then cure 4h at 80 DEG C to get to a kind of binary interpenetrating networks composite foam material containing side hydrogen bond group and boric acid estersil key Material.
This foamed material has good chemical resistance, can replace polymer material obtained as glassware Dai Pin, hard packing box, dalle are used, and have toughness and durability, while having good biodegradable Property.
Embodiment 12
(1) by the poly- Methyl Hydrogen Polysiloxane Fluid of methoxy group and a certain amount of Tert-butyl Methacrylate, O- isobutyl groups-N- Allyl thiocarbamate mixes, and active hydrogen atom (is directly connected with Si in poly- Methyl Hydrogen Polysiloxane Fluid in control reaction Hydrogen atom) molal quantity and Tert-butyl Methacrylate, O- isobutyl group-N- allyl thiocarbamates in double bond molal quantity Ratio be about 4:3:1, addition reaction occurs using chloroplatinic acid as catalyst, organic poly- silica containing side hydrogen bond group is made Alkane.
The above-mentioned organopolysiloxanes containing side hydrogen bond group of 60g and (the 2- methoxyl groups of 100g tri- are added in three-necked flask Ethyl) borate mixing, it is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, be added dropwise to a small amount of acetic acid, stirring It mixes and carries out polymerisation under state, a kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared, as 1st network polymer.
(2) methyl -3,3 hydroxy-end capped 50g, 3- trifluoro propyls polysiloxanes and the mixing of 80g trimethylborates, are warming up to 80 DEG C after mixing, swells in the 1st network polymer, adds the deionized water of 4ml, 5.3g white carbons, 6.1g titanium whites Powder, 3.2g di-iron trioxides, 0.2g carbon nanotubes, carry out polymerisation under stirring, and one kind is prepared and contains side hydrogen The dynamic aggregation object of key group and boric acid estersil key.
The polymeric articles have certain viscoplasticity, and colloidal state is presented, and sample surfaces are smooth, soft, have good time Elastic and certain compression strength, and a degree of stretching can be carried out.It is made into 80.0 × 10.0 × (2.0~4.0) mm The dumbbell shape batten of size carries out extension test using cupping machine, and rate of extension 50mm/min measures sample and stretches by force Degree is 6.28 ± 1.44MPa, and stretch modulus is 11.16 ± 1.75MPa, and elongation at break is 423 ± 148%.With blade poly- After closing object surface scratch, it will be bonded at cut, be placed in 80 DEG C of baking ovens and place 6h, cut can selfreparing.
Embodiment 13
(1) by the poly- diethyl containing hydrogen silicone oil and a certain amount of tert-butyl acrylate, 1- (3- pyrrolidines of ethyoxyl sealing end Base) mixing of -2- propylene -1- ketone, (hydrogen being directly connected with Si is former for active hydrogen atom in poly- diethyl containing hydrogen silicone oil in control reaction Son) molal quantity and Tert-butyl Methacrylate, 2- (2- oxygen -1- imidazolidinyls) ethyl methacrylate in double bond molal quantity Ratio is about 4:3:1, addition reaction occurs using chloroplatinic acid as catalyst, organic poly- silica containing side hydrogen bond group is made Alkane.
5- Aminopentyls dimethyl methoxy silane and three-butyl boron dihydroxide esters are mixed according to equimolar ratio, are 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.
The above-mentioned organopolysiloxane containing side hydrogen bond group and the above-mentioned boric acid ester compound containing boric acid estersil key are pressed According to end Si-OCH3The molar ratio 1 of group and B-OR groups:1 mixing, is added dropwise to 20% a small amount of acetic acid aqueous solution, in 50 DEG C of items After being stirred evenly under part, then it is added dropwise to the triethylamine of 2ml, the reaction was continued 4h is prepared and a kind of containing side hydrogen bond group and boron The dynamic aggregation object of sour estersil key, as the 1st network polymer.
(2) a certain amount of 5- cyclo-octene -1,2- glycol and 2- imidazolidinone -4- carboxylic acids are mixed, both control molal quantity Ratio be about 1:2, using bicyclic ethyl carbodiimide and 4-dimethylaminopyridine as catalyst, dichloromethane is solvent, is obtained The monomer 13a of hydrogen bonds group.
The monomer 13a of a certain amount of hydrogen bonds group and cyclo-octene are mixed and are dissolved in dichloromethane, both control molal quantity Ratio be about 1:2, and the nanometer titanium dioxide of the 1st network polymer and 5mg grain sizes 25nm relative to monomer 80wt% is added Silicon so that olefinic monomer is swollen in the 1st network polymer, under second generation Grubbs catalyst effect, is obtained one kind and is contained The dynamic aggregation object of hydrogen bond group and boric acid estersil key.
The polymer samples not only embody very excellent tensile toughness, also have good plasticity and resilience； Product of different shapes can be prepared into according to die size, after pressing its surface, recess can reply rapidly.It can It is made into all kinds of sealing element.
Embodiment 14
(1) poly- methyl trifluoro propyl-methylhydrogen silicone of methoxy group and a certain amount of allylamine are mixed, control Make mole of active hydrogen atom (hydrogen atom being directly connected with Si) in poly- methyl trifluoro propyl-methylhydrogen silicone in reaction The ratio of double bond molal quantity is about 1 in number and allylamine:1, addition reaction occurs using chloroplatinic acid as catalyst, obtained side group contains There are the methyl-silicone oil of polyamino group, i.e., a kind of poly-organosilicon polyamine.
It is 1 that above-mentioned poly-organosilicon polyamine and 2- furfuryl group isothiocyanates, which are pressed amino and isocyanates molar ratio,:1 is mixed It closes, using triethylamine as catalyst, reacts in methylene chloride, obtained side group contains thiourea group and trimethoxy silane group Organopolysiloxane.
Above-mentioned side group contains thiourea group organopolysiloxane and boric acid according to Si-OCH3Mole of group and B-OH groups Than 1:1 mixing, is warming up to 80 DEG C after mixing, adds a small amount of water, polymerisation is carried out under stirring, is prepared A kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key, as the 1st network polymer.
(2) by allyl hydroxyethyl ether and 5- chloromethyl -2- oxazolidones in molar ratio 1:1 is dissolved in toluene, with potassium carbonate For catalyst, tetrabutylammonium bromide is consisting of phase-transferring agent, obtains the olefinic monomer 14a containing oxazolidone group.
Under the conditions of anhydrous and oxygen-free, by allyl mercaptan and 2- thiophene isocyanates in molar ratio 1:1 is dissolved in dichloromethane, three Ethamine is catalyzed, and obtains the olefinic monomer 14b containing thio carbamate groups.
Olefinic monomer 14a, olefinic monomer 14b in molar ratio 50:50 are sufficiently mixed, and 80 parts of epoxidized soybean oils, stirring is added It after being sufficiently mixed, swells in the 1st network polymer, adds the AIBN of 5mol%, one is prepared by free radical polymerization The dynamic aggregation object organogel of epoxy soybean oil swell of the kind containing side hydrogen bond group and boric acid estersil key.
In the present embodiment, the polymer organic gel of the epoxy soybean oil swell has not only embodied preferable mechanical property Can, and with can selfreparing, pH response etc. functional characteristics.Obtained organogel has excellent toughness, in outer force effect The network structure of lower gel can't be damaged.Dynamic aggregation object gel can rely on its unique mechanical property, flexibility and Permeability is widely used in targeted drug release, fields are adsorbed and detached etc. to cell separation with label, protein.
Embodiment 15
(1) acetyl bromide of acrylic acid 2- amino-ethyls ester and equimolar equivalent is dissolved in dichloromethane, is catalyzed in triethylamine Under obtain acrylic acid 2- acetylamino ethyl esters.
Poly dimethyl-methyl hydrogen siloxane (PHMS, molecular weight 8000) and acrylic acid 2- acetylamino ethyl esters are mixed, control Make the molal quantity and propylene of active hydrogen atom (hydrogen atom being directly connected with Si) in poly dimethyl-methyl hydrogen siloxane in reaction The ratio of double bond molal quantity is about 1 in sour 2- acetylaminos ethyl ester:1, addition reaction occurs using chloroplatinic acid as catalyst, is made Side group contains the organopolysiloxane of hydrogen bond group, as the 1st network polymer.
(2) by poly dimethyl-methyl vinyl silicone of methoxy group (molecular weight about 3000) and 4- sulfydryl -2- pyrroles Pyrrolidone is according to double bond and the molar ratio of sulfydryl 1:1 mixing, is added the photoinitiator benzoin dimethylether (DMPA) of 0.2wt%, After stirring fully, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, a kind of organic poly- silica containing side hydrogen bond group is prepared Alkane.
The above-mentioned organopolysiloxane containing side hydrogen bond group and boric acid are according to Si-OCH3Mole of group and B-OH groups Than 1:1 mixing, is warming up to 80 DEG C after mixing, and 100mL1- butyl -3- methylimidazole hexafluorophosphates ([C is added4MIM] PF6) ionic liquid, the 1st network is fully swollen in, 45mg graphenes and a small amount of water are added, is polymerize under stirring Reaction, is prepared a kind of high strength ionic liquid dynamic aggregation object gel containing side hydrogen bond group and boric acid estersil key.
The modulus of the ionic liquid gel can reach 27 times in 32kPa, strain, and fracture strength is in 176kPa.This product It can be used in fine mold as stress loading material, while playing the role of bearing stress, and be had centainly Deformability plays cushioning effect, when its is cracked or damaged, can also be repaired by heating.
Embodiment 16
(1) by the poly dimethyl of methoxy group-phenyl hydrogen-containing siloxane (PHMS, molecular weight 4500) and 3- allyls- 2-Pyrrolidone mixes, and (hydrogen being directly connected with Si is former for poly dimethyl-phenyl hydrogen-containing siloxane active hydrogen atom in control reaction Son) molal quantity and 3- allyls -2-Pyrrolidone in the ratio of double bond molal quantity be about 1:1, using chloroplatinic acid as catalyst Addition reaction occurs, obtained side group contains the organopolysiloxane of hydrogen bond group.
The above-mentioned organopolysiloxane containing side hydrogen bond group and trimethylborate are according to Si-OCH3Group and B-OR groups Molar ratio 1:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, and carries out polymerizeing under stirring anti- It answers, a kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared, as the 1st network polymer.
(2) by poly dimethyl-methyl vinyl silicone of methoxy group (molecular weight about 5000) and N- phenyl -3- mercaptos Base propionamide is according to double bond and the molar ratio of sulfydryl 1:1 mixing, is added the photoinitiator benzoin dimethylether of 0.2wt% (DMPA), after stirring fully, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains being prepared a kind of containing side hydrogen bond group Organopolysiloxane.
The above-mentioned organopolysiloxane containing side hydrogen bond group and benzyl dihydro borate are according to Si-OCH3Group and B-OR The molar ratio 1 of group:1 mixing, fully swells in the 1st network polymer, is warming up to 80 DEG C after mixing, is added 4ml's Deionized water, then it is added dropwise to a small amount of acetic acid, continuation is stirred to react 4h in nitrogen atmosphere, and one kind is prepared and contains side hydrogen bond The binary interpenetrating networks dynamic aggregation object of group and boric acid estersil key.
The polymer samples not only embody certain intensity, but also show very excellent toughness, can be made It is used for a kind of sealing strip, sealing ring or elastic buffer gasket；In use, material shows good viscous Elasticity has good isolation vibrations and stress buffer effect, while also showing excellent hydrolytic resistance.When its surface goes out When existing damaged, the healing of breakage can be achieved to be molded again by heating, realize the selfreparing and recycling of material.
Embodiment 17
(1) by the poly dimethyl of methoxy group-methyl hydrogen silicone oil (PHMS, molecular weight 6000) and 5- (2- acrylic sulphur Base) mixing of -2,4 (1H, 3H)-hybar Xs, poly dimethyl-methyl hydrogen silicone oil active hydrogen atom (direct and Si in control reaction Connected hydrogen atom) molal quantity and 5- (2- acrylic sulfenyl) -2,4 (1H, 3H)-hybar Xs in double bond molal quantity ratio About 1:1, addition reaction occurs using chloroplatinic acid as catalyst, obtained side group contains hydrogen bond group and trimethoxy silane group Organopolysiloxane.
The above-mentioned organopolysiloxane containing side hydrogen bond group and trimethoxy silane group and triethyl borate are according to Si- OCH3The molar ratio 1 of group and B-OR groups:1 mixing, is warming up to 80 DEG C after mixing, the deionized water of 4ml is added, stirring It mixes and carries out polymerisation under state, a kind of dynamic aggregation object containing side hydrogen bond group and boric acid estersil key is prepared, as 1st network polymer.
(2) 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 is added, after being stirred evenly under the conditions of 50 DEG C, react 6h, a kind of dynamic containing boric acid estersil key is prepared Polymer, as the 2nd network polymer.
(3) 4- diallyls aminophenyl N- methyl carbamates and bis- (2- mercaptoethyls) ethers are according to molar ratio 1:1 It is sufficiently mixed, swells in the 1st network polymer and the 2nd network polymer, add relative to the light-initiated of monomer 0.2wt% Agent benzoin dimethylether (DMPA) and the talcum powder that 1g grain sizes are 50nm, are placed on ultraviolet radioactive 8h in UV crosslinking instrument, you can To a kind of ternary network interpenetrating dynamic aggregation object containing side hydrogen bond group and boric acid estersil key.
The polymeric articles surface is smooth, has certain case hardness, is broken after breaking, observes that glass micro-fibers exist It is evenly distributed in matrix, section, which is glued and placed in placement 12h in 120 DEG C of baking ovens, (may be selected to carry out slightly section during this Wetting), material can be molded again, compared to traditional epoxy resin cure material, embody recuperability.In this implementation In example, polymer material can be used to make electrical switchgear, zero of printed wiring chassis, instrument board electronic package material Part, it can also be used to which the fixation of various electronic components and metal parts, during use, polymer material have longer make Use the service life.
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 (17)

1. a kind of dynamic aggregation object or composition with hydridization bonding structure, which is characterized in that wherein include with dynamic Inorganic Boron Sour estersil key (B-O-Si) and the polymerization of optional Inorganic Boron oxygen boron key (B-O-B) or crosslinking polymerize and are moved made of being crosslinked simultaneously State covalent polymer ingredient, wherein any one B atom are connect with three-O-, connect at least two B atoms any one two Valence or the above linker of divalent are (poly-) siloxy group and optional-O-；Dynamic aggregation object molecule wherein at least described in part Upper to carry hydrogen bond group, the hydrogen bond group participates in forming hydrogen bond.
2. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that wherein, The hydrogen bond group contains hydrogen bond receptor or contains hydrogen bond donor or contain hydrogen bond receptor and hydrogen bond donor simultaneously.
3. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that wherein, The hydrogen bond receptor contains at least one of structure shown in the following general formula,
Wherein, A is selected from oxygen atom, sulphur atom；D is selected from nitrogen-atoms and C-R groups；X is halogen atom；Wherein, it is former to be selected from hydrogen by R Son, substitution atom, substituent group；
Wherein, the hydrogen bond donor contains at least one of structure shown in the following general formula,
4. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is non- Cross-linked structure, wherein being not up to gel point under inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key and hydrogen bond collective effect Above cross-linked structure.
5. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is friendship It is coupled structure, wherein the sum of inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key do not reach in the dynamic covalent polymer ingredient Dynamic covalent cross-linking more than to gel point；It excludes outside inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, in composition Hydrogen bond is not up to the hydrogen bond crosslinks of gel point or more；But in inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key and hydrogen bond Contain the cross-linked structure for reaching gel point or more in polymer composition under collective effect.
6. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is friendship It is coupled structure, wherein inorganic boric acid estersil key and optional Inorganic Boron oxygen boron bonding meter do not reach in the dynamic covalent polymer ingredient Dynamic covalent cross-linking more than to gel point；After excluding inorganic boric acid estersil key and optional Inorganic Boron oxygen boron key, in composition Hydrogen bond action is more than the gel point of hydrogen bond crosslinks.
7. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is friendship It is coupled structure, wherein the dynamic that inorganic boric acid estersil key reaches gel point or more in the dynamic covalent polymer ingredient is covalently handed over Inorganic Boron oxygen boron key is not present in connection；After excluding inorganic boric acid estersil key, the gel point of hydrogen bond action in composition in hydrogen bond crosslinks Below.
8. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is friendship It is coupled structure, wherein inorganic boric acid estersil key and Inorganic Boron oxygen boron key amount to gel point in the dynamic covalent polymer ingredient Above dynamic covalent cross-linking, inorganic boric acid estersil key is more than the gel point of dynamic covalent cross-linking；Exclude inorganic boric acid estersil After key and Inorganic Boron oxygen boron key, hydrogen bond action is below the gel point of hydrogen bond crosslinks.
9. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is friendship It is coupled structure, wherein the dynamic that inorganic boric acid estersil key reaches gel point or more in the dynamic covalent polymer ingredient is covalently handed over Inorganic Boron oxygen boron key is not present in connection；After excluding inorganic boric acid estersil key, the hydrogen bond action in composition is also in the gel of hydrogen bond crosslinks Or more.
10. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it is Cross-linked structure, wherein inorganic boric acid estersil key and Inorganic Boron oxygen boron key amount to gel in the dynamic covalent polymer ingredient Or more dynamic covalent cross-linking, inorganic boric acid estersil key is more than the gel point of dynamic covalent cross-linking；Exclude inorganic boric acid silicon After ester bond and Inorganic Boron oxygen boron key, hydrogen bond action is also more than the gel point of hydrogen bond crosslinks.
11. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that wherein Hydrogen bond group is carried in the side group or side chain or side group and side chain of at least partly described (poly-) siloxy group.
12. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that wherein Hydrogen bond group is carried in the side group or side chain or side group and side chain of at least partly described (poly-) siloxy group；Inorganic boric acid estersil key With the sum of optional Inorganic Boron oxygen boron key below the gel point of dynamic covalent cross-linking.
13. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that wherein Hydrogen bond group is carried in the side group or side chain or side group and side chain of at least partly described (poly-) siloxy group；Inorganic boric acid estersil key Reach the dynamic covalent cross-linking of gel point or more.
14. dynamic aggregation object or composition according to claim 1 with hydridization bonding structure, which is characterized in that it has There is following any character：Solution, lotion, cream, gel, ordinary solid, elastomer, foam.
15. the dynamic aggregation object or composition with hydridization bonding structure according to any one of claim 1-14, special Sign is that the recipe ingredient for constituting dynamic aggregation object or composition further includes following any or appoints several：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, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, breast Agent, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, levelling agent；
Wherein, the filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.
16. the dynamic aggregation object or composition with hydridization bonding structure according to any one of claim 1-14, special Sign is, is applied to following product：Damper, padded coaming, acoustic material, deadener, defense of resistance to impact material, movement Protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, bulletproof glass interlayer Glue, toughness material, shape-memory material, sealing element, toy, force snesor.
17. a kind of method of energy-absorbing, which is characterized in that a kind of dynamic aggregation object or composition with hydridization bonding structure are provided, And energy-absorbing is carried out using it as energy-absorbing material, wherein comprising with dynamic in dynamic aggregation object or composition with hydridization bonding structure Inorganic boric acid estersil key (B-O-Si) and optional Inorganic Boron oxygen boron key (B-O-B) polymerization crosslinking or simultaneously polymerize and be crosslinked and At dynamic covalent polymer ingredient, wherein any one B atom connect with three-O-, at least two B atoms of connection it is arbitrary One divalent or the above linker of divalent are (poly-) siloxy group and optional-O-；Dynamic aggregation wherein at least described in part Hydrogen bond group is carried on object molecule, the hydrogen bond group participates in forming hydrogen bond.
CN201710056040.1A 2017-01-25 2017-01-25 A kind of dynamic aggregation object or composition and its application with hydridization bonding structure Pending CN108341955A (en)

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