CN108341958A - A kind of energy-absorbing method based on hydridization dynamic aggregation object - Google Patents

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

Info

Publication number
CN108341958A
CN108341958A CN201710055918.XA CN201710055918A CN108341958A CN 108341958 A CN108341958 A CN 108341958A CN 201710055918 A CN201710055918 A CN 201710055918A CN 108341958 A CN108341958 A CN 108341958A
Authority
CN
China
Prior art keywords
atom
boron
key
inorganic
bond
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710055918.XA
Other languages
Chinese (zh)
Inventor
不公告发明人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Daimeng Sports Technology Co.,Ltd.
Original Assignee
Weng Qiumei
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Weng Qiumei filed Critical Weng Qiumei
Priority to CN201710055918.XA priority Critical patent/CN108341958A/en
Publication of CN108341958A publication Critical patent/CN108341958A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/04—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing boron

Abstract

The invention discloses a kind of energy-absorbing methods based on hydridization dynamic aggregation object.The hydridization dynamic aggregation object is simultaneously containing one or more in boric anhydride dynamic covalent bond existing for organic boronic ester bond and inorganic borate key and selectivity or supermolecule hydrogen bond.Dynamic reversibility based on boracic dynamic covalent bond and supermolecule hydrogen bond, the functions such as good damping, damping, sound insulation, shock resistance can be provided by being used using hydridization dynamic aggregation object as energy-absorbing material, be especially applied to movement and the body protection of daily life and work, army and police's body protection, explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact etc..

Description

A kind of energy-absorbing method based on hydridization dynamic aggregation object
Technical field
The present invention relates to a kind of energy-absorbing methods, and in particular to a kind of energy-absorbing method based on hydridization dynamic aggregation object.
Background technology
In the activity such as daily life, movement, amusement and recreation, military affairs, police service, security, medical care, production, human body, animal body It is often subject to seriously affecting for the physical impacts such as shock, vibration, vibrations, explosion, sound with article etc..By using energy-absorbing material Energy-absorbing is carried out, the effective protection to this kind of physical impact can be played, alleviated.These energy-absorbing methods are divided into active energy-absorbing and quilt Dynamic formula energy-absorbing.Active energy-absorbing includes using the methods of damper, and passive type energy-absorbing includes using the material with energy-absorbing function The methods of.Material for energy-absorbing mainly has the materials such as metal, polymer, composite material.Wherein, the energy damage of polymer material Consumption source is mainly the following：1, have near its glass transition temperature using polymer and is inhaled the phenomenon that high fissipation factor Energy.For this method since material is near glass transition temperature, the mechanical property of material is sensitive to temperature change, is using The mechanical property of the process in which materials easily acute variation with the variation of environment temperature, difficulty is brought to using.2, utilize covalent bond The fracture of equal chemical bonds and material internal crack the even processes energy-absorbing such as fracture of material entirety.In above-mentioned each process In, the fracture of covalent bond can not only restore with the crackle of macroscopic view, fracture, also the mechanical property of material will be caused to reduce.One After secondary or a small number of endergonic process several times, material must be replaced in time could maintain original performance.3, it is especially poly- using deformation Close the interior friction energy-absorbing between molecule segment caused by the relatively large deformation of object rubbery state or viscoelastic state.This method usually requires material Larger deformation, which occurs, for material could generate significant effect, and after the deformation of energy height loss occurs for material, it often can not be extensive Original shape is arrived again, can not be continuing with, it is necessary to be replaced.
In the prior art, the common structure of polymer material for being used as energy-absorbing has based on above-mentioned various energy loss mechanism And design obtained polymer alloy, polymer interpenetration network, polymer elastomer etc..These are often for structures of energy-absorbing The simple superposition of above-mentioned each mechanism, although expanding energy-absorbing range to a certain extent compared with single above-mentioned mechanism improves suction Energy efficiency, but still its deficiency can not be avoided.
Therefore, it is necessary to develop a kind of new energy-absorbing method, in particular with a kind of new energy absorption of introducing and loss machine The polymer of reason carries out energy-absorbing, to solve problems of the prior art.
Invention content
The present invention is directed to above-mentioned background, provides a kind of energy-absorbing method based on hydridization dynamic aggregation object, and the hydridization is dynamic State polymer contains organic boronic ester bond and inorganic borate key and optional organic boron acid anhydride key, Inorganic Boron acid anhydride key, has simultaneously It is one or more in machine-Inorganic Boron acid anhydride key or supermolecule hydrogen bond, using with reversible boracic dynamic key and supermolecule hydrogen Main means of the fracture of key as energy-absorbing.
The present invention is achieved by following technical solution：
A kind of energy-absorbing method based on hydridization dynamic aggregation object provides a kind of hydridization dynamic aggregation object, and using it as suction Energy material carries out energy-absorbing, and the hydridization dynamic aggregation object contains at least one organic boronic ester bond simultaneously and at least one is inorganic Boric acid ester bond；Wherein the organic boronic ester bond contains at least one comprising structure, the inorganic boric acid shown in formula (1) Ester bond contains at least one comprising structure shown in formula (2)：
Wherein, X is selected from carbon atom or silicon atom；K1、K2It is former to be each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine Son, iodine atom, oxygen atom, sulphur atom, boron atom, nitrogen-atoms, silicon atom, and K1、K2In it is at least one former selected from sulphur atom, boron Son, nitrogen-atoms, silicon atom；A is and K1、K2ConnectedNumber, work as K1、K2It is former for hydrogen atom, fluorine atom, chlorine atom, bromine When son, iodine atom, a 0, there is no the connections other than being connect with boron atom；Work as K1、K2For oxygen atom, sulphur atom when, a 1；When K1、K2For boron atom, nitrogen-atoms when, a 2；Work as K1、K2For silicon atom when, a 3；Wherein,It is expressed as in group and connection At least one；The organic boronic ester bond and inorganic borate key are hydridization dynamic aggregation object molecule aggregation or polymerization and friendship The tie point of connection.
In one embodiment of the invention, the organic boronic ester bond contained by the hydridization dynamic aggregation object is selected from At least one of organic boronic monoester bond, organic boronic cyclic ester key, organic boronic estersil key, contained inorganic borate key Selected from least one of organic boronic monoester bond, organic boronic cyclic ester key, organic boronic estersil key；
Wherein, the organic boronic monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；L be except direct key (including singly-bound, double bond, three keys), methylene or by The linker of at least divalent other than substituted methylene；
Wherein, the organic boronic cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular organic boronic ester units, the boron in the structure with two oxygen atoms simultaneously Atom need to be connected with a carbon atom by boron carbon key, and at least one organic group is keyed to boron original by the boron carbon On son；
Wherein, the organic boronic estersil key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；
The wherein Inorganic Boron acid monoester key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is connected with a carbon atom by boron carbon key；L is except direct key (including list Key, double bond, three keys), the linker of at least divalent other than methylene or substituted methylene；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently Selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and same formula In at least one Z atoms be selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When When Z is sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
The wherein inorganic boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular inorganic borate unit, the boron in the structure with two oxygen atoms simultaneously Atom is not connected directly with any carbon atom；Z atoms are selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；B is to be connected with ZNumber, when Z be sulphur atom when, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；Its In, linker L0It is each independently the position being connected with oxygen atom such as any one of lower structure, wherein * expressions：
The wherein inorganic boric acid estersil key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；When containing more than one in same formula The Z atomic time, each Z atoms are respectively independent；It is former that each Z atoms are each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine Son, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and at least one Z atoms are selected from sulphur atom, boron in same formula Atom, nitrogen-atoms, silicon atom；B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine Atom, b 0；When Z is sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3.
In one embodiment of the invention, the borate dynamic covalent bond contained by the hydridization dynamic aggregation object Combination include at least one of following combination：The combination of organic boronic monoester bond and Inorganic Boron acid monoester key, organic boronic list The combination of ester bond and inorganic boric acid cyclic ester key, the combination of organic boronic monoester bond and inorganic boric acid estersil key, organic boronic cyclic ester The combination of key and Inorganic Boron acid monoester key, the combination of organic boronic cyclic ester key and inorganic boric acid cyclic ester key, organic boronic cyclic ester key With the combination of inorganic boric acid estersil key, the combination of organic boronic estersil key and Inorganic Boron acid monoester key, organic boronic estersil key and The combination of inorganic boric acid cyclic ester key.
In one embodiment of the invention, the borate dynamic covalent bond contained by the hydridization dynamic aggregation object Combination include at least one of following combination：The combination of aminomethyl phenyl boric acid cyclic ester key and Inorganic Boron acid monoester key, aminomethyl The combination of phenyl boric acid monoester bond and inorganic boric acid cyclic ester key, the combination of aminomethyl phenyl boric acid monoester bond and Inorganic Boron acid monoester key, The combination of aminomethyl phenyl boric acid cyclic ester key and inorganic boric acid cyclic ester key, the group of organic boronic estersil key and Inorganic Boron acid monoester key It closes, the combination of organic boronic monoester bond and inorganic boric acid estersil key, the combination of organic boronic estersil key and inorganic boric acid cyclic ester key, The combination of organic boronic cyclic ester key and inorganic boric acid estersil key；
Wherein, the aminomethyl phenyl boric acid monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；L be except direct key (including singly-bound, double bond, three keys), methylene or by The linker of at least divalent other than substituted methylene；
The wherein aminomethyl phenyl boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom.
In one embodiment of the invention, in the hydridization dynamic aggregation object also contain boric anhydride dynamic covalent bond, At least one of dynamic supermolecule hydrogen bond；Wherein, the boric anhydride dynamic key is selected from organic boron acid anhydride key, Inorganic Boron acid anhydride key and has Machine-Inorganic Boron acid anhydride key；
Wherein, the organic boron acid anhydride key, for such as lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；
Wherein, the Inorganic Boron acid anhydride key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently Selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and same formula In at least one Z atoms be selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When When Z is sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；；
Wherein, the organic and inorganic boric anhydride key, selected from such as at least one of lower structure：
Wherein, one of boron atom is connected directly at least one carbon atom by boron carbon key in the structure, and extremely A few organic group is connected by the boron carbon key of formation with boron atom；Another boron atom is not former with any carbon in the structure Son is connected directly；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently Selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and same formula In at least one Z atoms be selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When When Z is sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
Wherein, the dynamic supermolecule hydrogen bond is by the hydrogen bond group phase interaction simultaneously containing hydrogen bond donor and hydrogen bond receptor With into.
In one embodiment of the invention, supermolecule hydrogen bond is contained in the hydridization dynamic aggregation object, and is formed The hydrogen bond group of supermolecule hydrogen bond contains at least one of following constituent：
In one embodiment of the invention, the glass transition temperature of the hydridization dynamic aggregation object each component is equal Not higher than 25 DEG C.
In one embodiment of the invention, the hydridization dynamic aggregation object has following any character：Solution, breast Liquid, cream, gel, ordinary solid, elastomer, foamed material.
In one embodiment of the invention, it further includes following to constitute the recipe ingredient of the hydridization dynamic aggregation object It is any or appoint it is several can additive or usable object：Other polymers, auxiliary agent, filler；Wherein, other polymers choosing From it is following any or appoint it is several：Natural polymer, synthetic resin, synthetic rubber, synthetic fibers；Wherein, described Auxiliary agent is selected from following any or appoints several：Catalyst, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat Stabilizer, emulsifier, fire retardant, chain extender, toughener, coupling agent, crosslinking agent, curing agent, solvent, lubricant, takes off dispersant Mould agent, plasticizer, thickener, thixotropic agent, levelling agent, colorant, fluorescent whitening agent, delustering agent, antistatic agent, fungus and mildew resistance Agent, foaming agent, nucleating agent, rheological agent, dynamic regulation agent；The filler is selected from following any or appoints several：Inorganic non-gold Belong to filler, metal packing, organic filler.
In one embodiment of the invention, the energy-absorbing method is applied to the body of movement and daily life and work Body protection, army and police's body protection, it is explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact, sound insulation, Damping.
A kind of hydridization dynamic aggregation object contains covalently at least one of the key combination of following borate dynamic simultaneously：Have The combination of machine boric acid monoester bond and Inorganic Boron acid monoester key, the combination of organic boronic monoester bond and inorganic boric acid cyclic ester key are organic The combination of boric acid monoester bond and inorganic boric acid estersil key, the combination of organic boronic cyclic ester key and Inorganic Boron acid monoester key, organic boron The combination of sour cyclic ester key and inorganic boric acid cyclic ester key, the combination of organic boronic cyclic ester key and inorganic boric acid estersil key, organic boronic The combination of estersil key and Inorganic Boron acid monoester key, the combination of organic boronic estersil key and inorganic boric acid cyclic ester key；Including boron Acid esters dynamic covalent bond is hydridization dynamic aggregation object molecule aggregation or polymerization and crosslinked tie point.
In one embodiment of the invention, the organic boronic monoester bond is aminomethyl phenyl boric acid monoester bond, institute The organic boronic cyclic ester key stated is aminomethyl phenyl boric acid cyclic ester key.
In one embodiment of the invention, the hydridization dynamic aggregation object also contains at least one boric anhydride dynamic altogether Valence link；Wherein, the boric anhydride dynamic covalent bond is selected from organic boron acid anhydride key, Inorganic Boron acid anhydride key, organic and inorganic boric anhydride key.
A kind of hydridization dynamic aggregation object contains at least one organic boronic ester bond and at least one inorganic borate simultaneously Key, and contain supermolecule hydrogen bond simultaneously；Organic boronic ester bond included in it and inorganic borate key are hydridization dynamic aggregations Object molecule aggregation or polymerization and crosslinked tie point；
Wherein the organic boronic ester bond contains at least one comprising structure, the inorganic boric acid shown in formula (1) Ester bond contains at least one comprising structure shown in formula (2)：
Wherein, X is selected from carbon atom or silicon atom；K1、K2It is former to be each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine Son, iodine atom, oxygen atom, sulphur atom, boron atom, nitrogen-atoms, silicon atom, and K1、K2In it is at least one former selected from sulphur atom, boron Son, nitrogen-atoms, silicon atom；A is and K1、K2ConnectedNumber, work as K1、K2It is former for hydrogen atom, fluorine atom, chlorine atom, bromine When son, iodine atom, a 0, there is no the connections other than being connect with boron atom；Work as K1、K2For oxygen atom, sulphur atom when, a 1；When K1、K2For boron atom, nitrogen-atoms when, a 2；Work as K1、K2For silicon atom when, a 3；Wherein,It is expressed as in group and connection At least one；
Wherein, the dynamic supermolecule hydrogen bond is by the hydrogen bond group phase interaction simultaneously containing hydrogen bond donor and hydrogen bond receptor With into.
In one embodiment of the invention, the supermolecule hydrogen bond contained in the hydridization dynamic aggregation object is by containing At least one hydrogen bond group of following constituent interacts：
In one embodiment of the invention, also contain in boric anhydride dynamic covalent bond in the hydridization dynamic aggregation object At least one；Wherein, the boric anhydride dynamic covalent bond is selected from organic boron acid anhydride key, Inorganic Boron acid anhydride key and organic and inorganic boric anhydride Key.
Compared with prior art, the invention has the advantages that：
(1) in the present invention, the borate dynamic covalent bond of energy-absorbing dynamic reversible present in hydridization dynamic aggregation object is real It is existing.On the one hand, outer masterpiece is being sheared and impacted to the borate dynamic covalent bond of the dynamic reversible contained in hydridization dynamic aggregation object Thickening effect can be generated under, and it is shock proof to play the role of energy-absorbing；On the other hand, when external force reaches a certain level, boric acid Ester dynamic covalent bond occurs to be broken a large amount of energy that can dissipate, and further functions as energy-absorbing function.Also, it in the present invention, uses The hydridization dynamic aggregation object for making energy-absorbing, it includes at least one organic boronic ester bonds and at least one inorganic borate key, i.e., extremely Few two kinds of boracic dynamic covalent bonds, and optional other kinds of boracic dynamic covalent bond.When polymer is broken by external force Bad when, the different boracic dynamic key of structure, to generate the dissipation step by step to power, can be conducive to carry with the variation of genetic sequence Tolerance and energy-absorbing effect of the high material to external force.Based on a variety of boracic dynamic covalent bonds of hydridization dynamic aggregation object in the present invention Multiple energy-absorbing mechanism is that the prior art is lacked, can be in a wider context to the dynamic of dynamic reversible key in energy-absorbing material It is combined collocation and regulation and control, obtains structure more horn of plenty, the energy-absorbing that performance is more various, dynamic reversible effect has more hierarchy Material.
(2) in the present invention, the hydridization dynamic aggregation object for being used as energy-absorbing also selectively contains dynamic supermolecule hydrogen bond.When When being destroyed by external force, supermolecule hydrogen bond is generally dissociated prior to boracic dynamic covalent bond polymer, is expanded to energy The range of absorption further enriches the multiple energy-absorbing mechanism of hydridization dynamic aggregation object.
(3) compared to other existing energy-absorbing methods, the present invention takes full advantage of boracic dynamic covalent bond and optional dynamic High dynamic invertibity possessed by state property supermolecule hydrogen bond, can without catalyst, without the condition of high temperature, illumination or specific pH It is lower to realize that the synthesis of hydridization dynamic aggregation object and dynamic reversibility also reduce while improving preparation efficiency using ring The limitation in border, make energy-absorbing material while can have the function of selfreparing etc., extend the application range of material.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific implementation mode
The present invention relates to a kind of methods of energy-absorbing, which is characterized in that provide a kind of hydridization dynamic aggregation object and using its as Energy-absorbing material carries out energy-absorbing；Wherein, the hydridization dynamic aggregation object contains at least one organic boronic ester bond and at least simultaneously A kind of inorganic borate key.
In the present invention, " energy-absorbing " refers to for including but not limited to shock, vibration, vibrations, explosion, sound institute Caused by physical impact energy absorption, do not include absorption only to thermal energy and/or electric energy.
Term " polymerization " used reaction is propagation process/effect of chain in the present invention, including reactant by polycondensation plus The process of product of the reaction formations such as poly-, the ring-opening polymerisation synthesis with higher molecular weight.Among these, reactant is typically The monomer of polymerizing power (can spontaneously be polymerize, or can be polymerize in initiator or outside plus under capable of acting on), The compounds such as oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds or two kinds with The product that upper reactant is polymerize is known as copolymer.It should be pointed out that " polymerization " in the present invention, packet The linear growth process of the chain containing reactant molecule includes the branched process of reactant molecule chain, including reactant molecule chain at Ring process also includes the cross-linking process of reactant molecule chain.
Term " crosslinking " used reaction in the present invention refers between reactant molecule and/or in reactant molecule by altogether Valence link is connected chemically to be formed with two dimension, three-dimensional cluster and the process for forming three-dimensional unlimited reticular pattern product in turn.It is being crosslinked In the process, polymer chain is general first constantly increases in two-dimensional/three-dimensional direction, and it (can be two dimension or three to gradually form cluster Dimension), developing deeply is three-dimensional infinite network.Unless stated otherwise, the present invention in cross-linked structure refer in particular to gel point or more (contain, under Three-dimensional infinite network structure together), non-crosslinked includes line style, branched, cyclic annular, two-dimentional cluster and gel point three-dimensional cluster knot below Structure isogel point structure below.
Heretofore described " gel point ", expression is reactant in cross-linking process, and viscosity is uprushed, and starts to coagulate Gelatinization phenomenon reaches reflecting point when a three-dimensional infinite network, also referred to as percolation threshold for the first time.Friendship more than gel point There is co-product three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer architecture；In solidifying Glue point cross-linking products below are only loose link structure, form three-dimensional infinite network structure, are only locally lying in A small amount of three-dimensional net structure, and it is not belonging to the cross-linked network that can constitute an entirety across entire polymer architecture.
In the present invention, " skeleton " refers to structure on the chain length direction of polymer chain.It is described for cross-linked polymer " main chain ", refer to the arbitrary segment being present in cross-linked network skeleton, i.e., connected in cross-linked network between adjacent crosslinking points Skeletal chain.For the polymer of non-crosslinking structure, " main chain " refers to the most chain of chain link if not otherwise indicated. Wherein, " side chain ", refers to that same main polymer chain is connected and is distributed in the chain structure of main chain side；Wherein, described " branch "/" bifurcated chain " can be side chain chain structures that can also be other come out from arbitrary chain bifurcated.Wherein, described " side group " refers to that the arbitrary chain of same polymer is connected and is distributed in the chemical group of chain side.Wherein, " end group ", Refer to that the arbitrary chain of same polymer is connected and positioned at the chemical group of chain end.If not otherwise indicated, side group refers in particular to be connected to Group of the molecular weight of polymer chain skeleton side no more than 1000Da and subunit group therein.When side chain, the molecule of bifurcated chain When amount is no more than 1000Da, itself and group thereon are considered as side group.For the sake of simplicity, when side chain, the molecular weight of bifurcated chain When more than 1000Da, if not otherwise indicated, then it is collectively referred to as side chain.Above-mentioned " side chain ", " side group " can have multilevel hierarchy, Namely side chain/side group can continue to carry side chain/side group, side chain/side group of side chain/side group can continue have side chain/side group.This In invention, for hyperbranched and dendroid chain and its relevant chain structure, the polymer segment of outermost can be considered as side chain, Remaining part point can be considered as main chain.
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 borate dynamic covalent bond " described in embodiments of the present invention refers to organic boronic ester bond and inorganic Boric acid ester bond；" the boric anhydride dynamic covalent bond " refers to organic boron acid anhydride key, Inorganic Boron acid anhydride key and organic and inorganic boric anhydride key； " the boracic dynamic covalent bond " refers to borate dynamic covalent bond and boric anhydride dynamic covalent bond.
Heretofore described " dynamic covalent cross-linking network ", refer to when dynamic covalently boracic dynamic covalent bond also by regarding For polymer polymerization linking point when can reach the polymer network of gel point or more；And when boracic dynamic all in system Covalent bond all disconnects, and when only being linked with common covalent bond, polymeric system is decomposed into following any or several lists Member：The units such as monomer, polymer chain segment, polymer cluster.Heretofore described " common covalent cross-linking network ", refers to When boracic dynamic covalent bond all in system all disconnects, when being only crosslinked with common covalent bond, gel still can be reached Or more polymer network.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention Can include to be selected from the option of the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
In embodiments of the present invention, the topological structure of the hydridization dynamic aggregation object molecule can be selected from but not limited to Line style, ring-type, branched (such as star-like, combed, H-type, dendritic, hyperbranched and combinations thereof), two-dimensional/three-dimensional cluster, three-dimensional are unlimited Network or with the combination for several structures of taking up an official post.Wherein, the structures such as side chain of polymer can have multilevel hierarchy.One polymer group Can only have a kind of hydridization dynamic aggregation object molecule of topographic morphologies in, can also be that there are many hydridization of topographic morphologies dynamics The mixture of polymer molecule.Wherein, the boracic dynamic covalent bond contained in hydridization dynamic aggregation object molecule polymerize once dissociating Objects system is decomposed into following any or several units：Monomer, small molecule group, polymer chain segment, polymer two Dimension/three-dimensional cluster；Meanwhile the bonding and dissociation of boracic dynamic covalent bond can be passed through between hydridization dynamic aggregation object and said units Realization mutually converts and dynamic reversible.It is with particularly pointing out, when the hydridization dynamic aggregation object is two-dimensional/three-dimensional cluster, The degree of cross linking does not have any restriction with cross-linked structure；When the topological structure of the hydridization dynamic aggregation object is three-dimensional infinite network, I.e. unlimited cross-linked network structure of the degree of cross linking more than gel point when, the structure is only dynamic covalent cross-linking net in the present invention Network, without including common covalent cross-linking network.
In the present invention, at least one that the hydridization dynamic aggregation object contains simultaneously includes structure shown in formula (1) Organic boronic ester bond and at least one inorganic borate key for including structure shown in formula (2)：
Wherein,Indicate any appropriate group and/or connection, including but not limited to any appropriate hydrogen atom, miscellaneous original The small molecule group of subbase group, molecular weight no more than 1000Da, polymer chain residue of the molecular weight more than 1000Da, molecular weight are not The connection that the inorganic macromolecular chain residue of inorganic molecules chain residue, molecular weight more than 1000Da more than 1000Da is connected, even Two on the same atomIt can be connected in simultaneously on another atom and form double bond, three be connected on the same atom It is aCan simultaneously be connected on another atom and form three keys, wherein any twoBe connected cyclic or not cyclic, described ring Can be selected from but be not limited only to aliphatic ring, ether ring, condensed ring or combinations thereof, the feelings such as a part for aromatic ring can also be connected to Condition.It is such when what is hereinafter occurred againAbove-mentioned definition and range are all continued to use, such as without special case, no longer carries out repeated explanation.Its In, X is selected from carbon atom or silicon atom.K1、K2Be each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, Oxygen atom, sulphur atom, boron atom, nitrogen-atoms, silicon atom, preferably oxygen atom, boron atom, nitrogen-atoms, and K1、K2In at least one It is a to be selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom.A is and K1、K2ConnectedNumber.Work as K1、K2For hydrogen atom, fluorine When atom, chlorine atom, bromine atom, iodine atom, a 0, there is no the connections other than being connect with boron atom；Work as K1、K2For oxygen atom, When sulphur atom, a 1；Work as K1、K2For boron atom, nitrogen-atoms when, a 2；Work as K1、K2For silicon atom when, a 3.Wherein, described Organic boronic ester bond and inorganic borate key are hydridization dynamic aggregation object molecule aggregation or polymerization and crosslinked tie point.
In embodiments of the present invention, organic boronic ester bond more specifically can include but is not limited to following at least one Structure：Organic boronic monoester bond, organic boronic cyclic ester key, organic boronic estersil key.
In embodiments of the present invention, the organic boronic monoester bond, may be selected from but not limited to as in lower structure At least one：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure；L is except direct key (packet Include singly-bound, double bond, three keys), the linker of at least divalent other than methylene or substituted methylene.(L is direct key, Asia Methyl or substituted methylene and the case where forming five-membered ring or hexatomic ring, are considered as organic boronic cyclic ester key in the present invention, no Including herein.) the organic boronic monoester bond passes throughIt accesses in polymer chain, can also be connect by atom/group on L Enter in polymer chain, atom/group on L can also on the C of its both sidesConnection cyclization.
In embodiments of the present invention, the organic boronic cyclic ester key, may be selected from but not limited to as in lower structure At least one：
Wherein, a boron atom forms cyclic annular organic boronic ester units, the boron in the structure with two oxygen atoms simultaneously Atom need to be connected with a carbon atom by boron carbon key, and at least one organic group is keyed to boron original by the boron carbon On son.
In embodiments of the present invention, the organic boronic estersil key, may be selected from but not limited to as in lower structure At least one：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom.
Wherein, since the dynamic response of organic boronic estersil key and aminomethyl phenyl boric acid cyclic ester key is strong, dynamic response item Part is mild, can without catalyst, without high temperature, illumination or specific pH under conditions of realize hydridization dynamic aggregation object synthesis, While improving preparation efficiency, the limitation of use environment is also reduced, extends the application range of polymer, therefore this The further preferred organic boronic estersil key of organic boronic ester bond and aminomethyl phenyl boric acid ester bond of invention.Wherein, the ammonia first Base phenyl boric acid ester bond is containing the aminomethyl phenyl boric acid monoester bond of at least one of structure shown in formula (6A)-(6C) and to contain The aminomethyl phenyl boric acid cyclic ester key of at least one of structure shown in formula (6D), (6E)：
Wherein, the definition of L, range of choice and preferred scope are as previously described.The organic boronic ester bond of the present invention is more preferably Organic boronic estersil key and aminomethyl phenyl boric acid cyclic ester key.
In the present invention, the inorganic boracic dynamic covalent bond can more specifically preferably be selected from as in lower structure at least It is a kind of：Inorganic Boron acid monoester key, inorganic boric acid cyclic ester key, inorganic boric acid estersil key.
The Inorganic Boron acid monoester key in the present invention, may be selected from but not limited to such as lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；L is the same as in above-mentioned organic boronic monoester bond Definition, range of choice and the preferred scope of L.When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent； It is former that each Z atoms are each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron Son, silicon atom, and at least one Z atoms are selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom in same formula.B is to be connected with Z 'sNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is sulphur atom, b 1； When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3.The Inorganic Boron acid monoester key passes throughAccess is poly- It closes in object chain, can also be accessed in polymer chain by the atom on L/group, atom/group on L can also be with its both sides C OnConnection cyclization.
The inorganic boric acid cyclic ester key in the present invention, may be selected from but not limited to such as lower structure：
Wherein, a boron atom forms cyclic annular inorganic borate unit, the boron in the structure with two oxygen atoms simultaneously Atom is not connected directly with any carbon atom；Z, the definition of b, range of choice and preferred scope are the same as in above-mentioned Inorganic Boron acid cyclic ester key Definition, range of choice and the preferred scope of corresponding Z, b；Linker L0It is each independently such as any one of lower structure, Middle * indicates the position being connected with oxygen atom：
The inorganic boric acid estersil key in the present invention, may be selected from but not limited to such as lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；Z, the definition of b, range of choice and excellent Select range with definition, range of choice and the preferred scope of corresponding Z, b in above-mentioned Inorganic Boron acid monoester key.
In embodiments of the present invention, the difference of different types of borate dynamic covalent bond chemical composition and adjacent have The difference of machine group can be that material strips carry out different performance, the organic boronic ester bond contained in hydridization dynamic aggregation object and inorganic The combination of boric acid ester bond can utilize the arbitrary reasonable manner of its performance difference, as an example, preferably following organic boric acid ester At least one of the combination of key and inorganic borate key：The combination of organic boronic monoester bond and Inorganic Boron acid monoester key, it is organic The combination of boric acid cyclic ester key and inorganic boric acid cyclic ester key, organic (or inorganic) boric acid monoester bond and inorganic (or organic) boric acid cyclic ester The combination of key, the combination of organic (or inorganic) boric acid monoester bond and inorganic (or organic) boric acid estersil key, organic (or inorganic) boron The combination of sour cyclic ester key and inorganic (or organic) boric acid estersil key.Wherein, aminomethyl phenyl boric acid cyclic ester key has faster external force Response speed, organic and inorganic boric acid estersil key can realize dynamic reversibility, therefore, this hair under conditions of room temperature is without catalyst The combination of the organic boronic ester bond and inorganic borate key that contain in bright hydridization dynamic aggregation object is shown under being more preferably At least one of the combination of machine boric acid ester bond and inorganic borate key：Aminomethyl phenyl boric acid cyclic ester key and Inorganic Boron acid monoester key Combination, the combination of aminomethyl phenyl boric acid monoester bond and inorganic boric acid cyclic ester key, aminomethyl phenyl boric acid cyclic ester key and inorganic boric acid The combination of cyclic ester key, the combination of organic (or inorganic) boric acid estersil key and inorganic (or organic) boric acid monoester bond, organic (or nothing Machine) boric acid estersil key and inorganic (or organic) boric acid cyclic ester key combination etc..In above-mentioned preferred combination, different types of boracic Otherness between dynamic covalent bond can carry out multiple energy-absorbing to material strips and respond effect.
In embodiments of the present invention, above-mentioned organic boronic ester bond and inorganic borate key can both be located at same point In son, it can also be located in different molecular.Wherein, position of the organic/inorganic boric acid ester bond in polymer molecule There is no any restriction, can be located on the arbitrary position of polymer molecule, such as main chain backbone, side chain skeleton, side group and/or end Base is preferably placed at polymer chain skeleton.
In embodiments of the present invention, organic boronic monoester bond, organic boronic cyclic ester key, organic boronic estersil key are preferred It is formed respectively with single hydrocarbon hydroxyl primitive, dihydroxy primitive, silicone hydroxyl elementary reaction by organic boronic primitive；Inorganic Boron acid monoester Key, inorganic boric acid cyclic ester key, inorganic boric acid estersil key are preferably respectively by inorganic boronate member and single hydrocarbon hydroxyl primitive, dihydroxy base Member, silicone hydroxyl elementary reaction form.
In the present invention, the organic boron acidic group primitive, boron atom passes through boron at least one carbon atom in structure Carbon key is connected directly, and at least one organic group is connected by the boron carbon key of formation with boron atom, is connected simultaneously in boron atom At least one boron hydroxyl or hydrolyzable form the group or atom of boron hydroxyl；The organic boron acidic group primitive can be selected from but unlimited In at least one of organic boron acidic group, organic boronic ester group, organic boronic alkali, organic boron alkylhalide group.
Wherein, the organic boron acidic group, preferably comprises such as at least one of lower structure：
Wherein, the organic boronic ester group, preferably comprises such as at least one of lower structure：
Wherein, R1、R2、R3For the monovalent organic group or monovalence organosilicon radical being connected directly with oxygen atom, pass through carbon Atom or silicon atom are connected directly with oxygen atom, are each independently selected from following any structure：Molecular weight is no more than The small molecule silylation of small molecule alkyl, molecular weight no more than 1000Da, the molecular weight of 1000Da are more than the polymer of 1000Da The small molecule alkyl of chain residue, preferably molecular weight no more than 1000Da, molecular weight are no more than the small molecule silylation of 1000Da, More preferably small molecule alkyl of the carbon atom number no more than 4 and molecular weight are no more than the small molecule silylation of 200Da；R4For with two The bivalent organic group or divalent organosilicon radical that a oxygen atom is connected directly are straight by carbon atom or silicon atom and oxygen atom Connect it is connected, be selected from following any structure：Divalent small molecule alkylene, molecular weight of the molecular weight no more than 1000Da are no more than Divalent small molecule silicylene, the molecular weight of 1000Da are more than the diatomic polymer chain residue of 1000Da, preferably molecular weight not Small molecule alkylene, molecular weight more than 1000Da are no more than the small molecule silicylene of 1000Da, more preferably methylene, Asia Ethyl, substituted methylene, substituted ethylidene and molecular weight are no more than the small molecule silylation of 200Da.
Wherein, the organic boronic alkali, preferably comprises such as at least one of lower structure：
Wherein, M is any appropriate metallic element or any appropriate ionic group in the periodic table of elements, and n is the valence of M Number, preferably+1 valence ,+divalent ,+trivalent, citing such as lithium ion, potassium ion, sodium ion, magnesium ion, calcium ion, iron ion, copper ion With ammonium ion etc..
Wherein, the organic boron alkylhalide group, preferably comprises such as at least one of lower structure：
Wherein, R5、R6、R7It is each independently selected from fluorine atom, chlorine atom, bromine atom, iodine atom.
As an example, suitable organic boron acidic group primitive is exemplified below, however, the present invention is not limited thereto：
Wherein, x, y are a fixed value or average value, and x is 0 or the integer more than or equal to 1, and y is whole more than or equal to 1 Number；It is preferred that be connected with other reactive groups, convenient for being accessed in hydridization dynamic aggregation object by common covalent bond, or with Connection structure G is connected, and forms the organic boronic base class raw material containing the organic boron acidic group primitive described in two or more, Can be at least one of micromolecular compound, oligomer, polymer.The connection structure G can be selected from following any Or appoint several：Singly-bound, divalent or multivalence hetero atom linker, molecular weight are no more than the divalent or multivalence small molecule hydrocarbon of 1000Da Base, molecular weight are more than the divalent or multivalence polymer chain residue of 1000Da.It is important to note that when G is selected from polymer chain When residue, selected polymer chain is also as the part in the hard section or soft segment or hard section or soft segment of hydridization dynamic aggregation object.
Specifically, when G is selected from singly-bound, boron boron singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon be can be selected from Singly-bound, boron nitrogen singly-bound；Preferably boron boron singly-bound, boron carbon single bond, carbon-carbon single bond.
When G is selected from hetero atom linker, it can be selected from following any or appoint several combinations：Ether, sulfenyl, thioether Base, divalent tertiary amine groups, trivalent tertiary amine groups, divalent silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalent phosphorus base, three valent phosphors base, divalent boron Base, trivalent boryl, preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups；When G is selected from molecular weight no more than 1000Da's When divalent or multivalence small molecule alkyl, 1 to 71 carbon atoms are typically contained, the valence state of alkyl can be 2-144 valences, can contain Heteroatom group, can be free of has heteroatom group.Generally, the divalent or multivalence small molecule alkyl can be selected from following Any in group, any unsaturated form, any substituted form or any by hydridization form：Two to one hundred 40 tetravalence C1-71Alkyl, two to one hundred four ten tetravalence ring C3-71Alkyl, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred 40 tetravalence aryls, preferably two to tetravalence methyl, two to sexavalence ethyl, two arrive octavalence propyl, and two arrive sexavalence cyclopropane base, two Sexavalence phenyl is arrived to octavalence cyclobutyl, two to ten valence cyclopenta, two to ten cyclohexyl radicals, two.
Can be any appropriate two when G, which is selected from molecular weight, is more than the divalent or multivalence polymer chain residue of 1000Da It is poly- to include but are not limited to divalent or multivalence carbochain polymer residue, divalent or multivalence heterochain for valence or multivalence polymer chain residue Close object residue, divalent or element of multivalence organic polymer residue；Wherein, polymer can be homopolymer, or several monomers, The copolymer of oligomer or polymer composition, polymer chain can be flexible chain or rigid chain.
When G is selected from divalent or multivalence carbochain polymer residue, can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, any taken For form or any by hydridization form：Divalent or multivalence polyolefins chain residue, as divalent or multivalence Polyethylene Chain residue, Divalent or multivalence polypropylene chains residue, divalent or multivalence polyisobutene chain residue, divalent or multivalence polystyrene chain residue, divalent Or multivalence polyvinyl chloride chain residue, divalent or multivalence Vingon chain residue, divalent or multivalence polyvinyl fluoride chain residue, divalent Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalent or multivalence polytrifluorochloroethylene chain residue, divalent or multivalence polyvinyl acetate chain Residue, divalent or multivalence polyvinyl alcohol chain residue, divalent or multivalence Polyvinylalkylethers chain residue, divalent or multivalence polybutadiene The poly- drop of alkene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polychlorobutadiene chain residue, divalent or multivalence Bornylene chain residue etc.；Divalent or multivalence polyacrylic chain residue, such as divalent or multivalence polyacrylic acid chain residue, divalent or more Valence polyacrylamide chain residue, divalent or multivalence polymethyl acrylate chain residue, divalent or multivalence polymethyl methacrylate chain Residue etc.；Divalent or multivalence polypropylene nitrile chain residue, such as divalent or multivalence polyacrylonitrile chain residue.G preferred divalent or more Valence Polyethylene Chain residue, divalent or multivalence polypropylene chains residue, divalent or multivalence polystyrene chain residue, divalent or multivalence polychlorostyrene Ethylene chain residue, divalent or multivalence polybutadiene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence poly- third Olefin(e) acid chain residue, divalent or multivalence polyacrylamide chain residue, divalent or multivalence polyacrylonitrile chain residue.
When G is selected from divalent or multivalence heterochain polymer residue, can be any appropriate macromolecular main chain mainly by The polymer residue that the hetero atoms such as carbon atom and nitrogen, oxygen, sulphur are constituted, can be selected from any in the following group, any insatiable hunger With form, any substituted form or any by hydridization form：Divalent or multivalence polyethers chain residue, such as divalent or Multivalence polyethylene oxide chain residue, divalent or multivalence polypropylene oxide chain residue, divalent or multivalence PolyTHF chain residue, two Valence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalent or multivalence phenolic resin chain residue, divalent or multivalence polyphenylene oxide chain residue etc.；Divalent Or multivalence polyesters chain residue, as divalent or multivalence polycaprolactone chain residue, the divalent or poly- valerolactone chain residue of multivalence, divalent or Multivalence polylactide chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence unsaturated polyester (UP) Chain residue, divalent or multivalence alkyd resin chain residue, divalent or multivalence polycarbonate chain residue etc.；Divalent or multivalence polyamine class chain Residue, as divalent or multivalence polyamide chains residue, divalent or multivalence polyimides chain residue, divalent or multivalence polyurethane chain are residual Base, divalent or multivalence polyureas chain residue, divalent or multivalence Lauxite chain residue, divalent or multivalence melamine resin chain residue etc..G It is preferred that divalent or multivalence polyethylene oxide chain residue, divalent or multivalence PolyTHF chain residue, divalent or multivalence epoxy resin Chain residue, divalent or multivalence polycaprolactone chain residue, divalent or multivalence polylactide chain residue, divalent or multivalence polyamide chains are residual Base, divalent or multivalence polyurethane chain residue.
Can be any appropriate macromolecular main chain master when G is selected from divalent or element of multivalence organic polymer residue The polymer residue to be made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, can be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalent or Multivalence silicone-based polymers chain residue, such as divalent or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane Chain residue, divalent or multivalence poly-organosilicon borine chain residue, divalent or multivalence poly-organosilicon azane chain residue, divalent or multivalence are poly- Organic silithiane chain residue, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or the poly- organic metal siloxane chain of multivalence Residue；Divalent or multivalence organic boron Type of Collective object chain residue, as the divalent or poly- organo-borane chain residue of multivalence, divalent or multivalence are poly- Organic boron azane chain residue, divalent or the poly- organic boron sulfane chain residue of multivalence, divalent or the poly- organic boron phosphine chain residue of multivalence etc.； Divalent or multivalence organic phosphates polymer chain residue；Divalent or multivalence Organic leadP Type of Collective object chain residue；Divalent or multivalence are organic Tin Type of Collective object chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain residue；Divalent or multivalence antimony organic Type of Collective object chain are residual Base.The preferred divalent of G or multivalence poly-organosilicon alkane chain residue, the divalent or poly- organo-borane chain residue of multivalence.
Wherein, other described reactive groups, referring to can spontaneously or can be in initiator or light, heat, spoke According to the group for carrying out chemical reaction under the conditions of, catalysis etc. and generating common covalent bond, suitable group includes but are not limited to：Hydroxyl Base, carboxyl, carbonyl, acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, sulfydryl, alkenyl, alkynyl, cyano, Piperazine base, oximido, diazanyl, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxy group, acrylate group, acrylamide Group, maleimide base group, succinimide ester groups, norbornene group, azo group, azido group, heterocyclic group, Triazoline diketone, carbon radicals, oxygen radical etc.；It is preferred that amino, sulfydryl, alkenyl, isocyanate groups, epoxy group, propylene Acid esters group, acrylamide group.
As an example, suitable organic boron base class raw material is exemplified below, however, the present invention is not limited thereto：
Wherein, x, y, z is each independently a fixed value or average value, is each independently selected from whole more than or equal to 1 Number.
In the present invention, the inorganic boronate primitive, boron atom is not connected directly with carbon atom in structure, can Selected from but not limited to inorganic boronate, Inorganic Boron perester radical, inorganic borate base, Inorganic Boron alkylhalide group, inorganic boryl.
Wherein, the inorganic boronate, refer in compound structure include at least one by boron atom and with The structural motif (B-OH) that a connected hydroxyl of the boron atom is formed, and the original being directly connected to boron atom in compound Son is selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, boron atom, nitrogen-atoms, oxygen atom, silicon atom, sulphur atom, It is preferred that bromine atom, chlorine atom, oxygen atom and boron atom.
Wherein, the Inorganic Boron perester radical is referred to including at least one in compound structure by boron atom and is somebody's turn to do Structural motif (the B-OR that a connected oxygen atom of boron atom and the alkyl or silylation that are connected with the oxygen atom are formed；Its Middle R is the alkyl based on carbon, hydrogen atom or the silylation based on silicon, hydrogen atom, passes through carbon atom or silicon atom and oxygen Atom be connected), and the atom being directly connected to boron atom in compound be selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, Iodine atom, boron atom, nitrogen-atoms, oxygen atom, silicon atom, sulphur atom, preferably bromine atom, chlorine atom, oxygen atom and boron atom.
Wherein, the inorganic borate base, refer to including at least in compound structure one by boron atom and Structural motif (the B-O that a negative oxygen ion being connected with the boron atom is formed-) and including at least a cation (Mn+), and And the atom being directly connected to boron atom in compound is selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, boron original Son, nitrogen-atoms, oxygen atom, silicon atom, sulphur atom, preferably bromine atom, chlorine atom, oxygen atom and boron atom.
Wherein, the Inorganic Boron alkylhalide group, refer to including at least in compound structure one by boron atom and The structural motif (B-F, B-Cl, B-Br, B-I) that a halogen atom (F, Cl, Br, I) being connected with the boron atom is formed, and And the atom being directly connected to boron atom in compound is selected from fluorine atom, chlorine atom, bromine atom, iodine atom, boron atom, nitrogen original Son, oxygen atom, silicon atom, sulphur atom, preferably bromine atom, chlorine atom, oxygen atom and boron atom.
Wherein, the inorganic boryl, refer in compound structure include at least one by boron atom and with The structural motif (B-H) that a connected hydrogen atom of the boron atom is formed.
As an example, suitable Inorganic Boron base class raw material includes but not limited to：Ortho-boric acid, metaboric acid, pyroboric acid, tetrahydroxy Two boron, trimethylborate, triethyl borate, tricyclohexyl borate, boric acid front three phenyl ester, three benzyl ester of boric acid, triphenyl borate, boron Sour triallyl, boric acid three (dodecyl) ester, boric acid three (octadecyl) ester, three tert-butyl ester of boric acid, phenyl-ethylene boric acid Ester, duplex pinacol borate, duplex catechol carbonic ester, duplex (2- methyl -2,4-PD) borate, duplex (2- Methyl -2,4-PD) borate, duplex (D- ethyl tartrates) borate, duplex (L-TARTARIC ACID diethylester) borate, Tetraphenyl five aoxidizes two boron, boron trifluoride, boron chloride, Boron tribromide, triiodide boron, four chlorinations, two boron, diborane, penta boron Alkane, boron oxide (B2O3), sodium borate decahydrate (borax), potassium pentaborate, hypoboric acid magnesium, single line borate, three barium borates, inclined boron Sour zinc, tetraboric acid diammonium, ammonium pentaborate, eight boric acid diammoniums etc..
In the present invention, single hydrocarbon hydroxyl primitive, may be selected from but not limited to single alkanol hydroxyl, monoene alcoholic extract hydroxyl group, Single phenol hydroxyl, at least four atom polyhydroxy chemical combination of the polyphenol hydroxyl in meta position, the polyphenol hydroxyl in contraposition and interval Hydroxyl in object.
Wherein, single alkanol hydroxyl refers to that with the carbon atom that hydroxyl is directly connected to be alkyl carbon atom, packet Include the alkane of hetero atom connection；The monoene alcoholic extract hydroxyl group refers to that with the carbon atom that hydroxyl is directly connected to be ethylenic unsaturation Alkyl carbon atom includes the alkene of hetero atom connection；The single phenol hydroxyl, refers to the carbon atom being directly connected to hydroxyl It is aromatic hydrocarbon carbon atom, including miscellaneous aromatic hydrocarbon；It, at least can be with if there are two or more single hydrocarbon hydroxyls in compound It is the hydroxyl at least four atom polyols of the polyphenol hydroxyl in meta position, the polyphenol hydroxyl in contraposition and interval Base.
As an example, suitable single hydrocarbon hydroxyl primitive is exemplified below, however, the present invention is not limited thereto：
Wherein, x, y are a fixed value or average value, and x is 0 or the integer more than or equal to 1, and y is whole more than or equal to 1 Number；It is preferred that being connected with other above-mentioned reactive groups, convenient for accessing hydridization dynamic aggregation object by common covalent bond In, or be connected with connection structure G, it is former to form single hydrocarbon hydroxyl primitive class containing the hydroxyl primitive described in two or more Material.Wherein, the definition of the connection structure G, range of choice, preferred scope are same as above.
As an example, suitable single hydrocarbon hydroxyl primitive class raw material is exemplified below, however, the present invention is not limited thereto：
Wherein, x, y, z, k are each independently a fixed value or average value, are each independently selected from more than or equal to 1 Integer.
In the present invention, the dihydroxy primitive can be selected from but be not limited only to 1,2- glycol-baseds, 1,3- glycol-baseds, neighbour two At least one of phenolic hydroxyl group and 2- hydroxymethyl phenol hydroxyls.
Wherein, 1, the 2- glycol-baseds can be selected from glycol molecule lose formed after at least one non-hydroxyl hydrogen atom it is residual Base；The 1,3- glycol-baseds can be selected from 1,3- propylene glycol molecules and lose the residue formed after at least one non-hydroxyl hydrogen atom；Institute The adjacent diphenol primitive stated can be selected from adjacent diphenol and lose the residue formed after non-hydroxyl hydrogen atom at least one aromatic ring；The 2- Methylol phenolic group can be selected from 2- hydroxymethyl phenols and lose the residue formed after at least one non-hydroxyl hydrogen atom.
As an example, suitable dihydroxy primitive includes but not limited to：
Wherein, x is a fixed value or average value, x >=1；It is preferred that be connected with other above-mentioned reactive groups, Convenient for being accessed in hydridization dynamic aggregation object by common covalent bond, or be connected with connection structure G, formed there are two containing or two with The dihydroxy primitive class raw material of the upper dihydroxy primitive.Wherein, the definition of the connection structure G, range of choice, preferably Range is same as above.
As an example, suitable dihydroxy primitive class raw material includes but not limited to：
Wherein, y is a fixed value or average value, for the integer more than or equal to 1.
In the present invention, the silicone hydroxyl primitive, refers at least one of silicone hydroxyl or silicone hydroxyl presoma.
Wherein, the silicone hydroxyl, the knot that a hydroxyl being connected by silicon atom and with the silicon atom is formed Structure primitive.Wherein, silicone hydroxyl can be that (silicon atom i.e. in silicone hydroxyl at least passes through silicon-carbon bonds to organic silicone hydroxyl with a carbon atom It is connected, and at least one organic group is keyed to by the silicon-carbon on silicon atom) or inorganic silicone hydroxyl (i.e. silicon Silicon atom in hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.
Wherein, the silicone hydroxyl presoma, refer to one be connected by silicon atom and with the silicon atom can water Solution obtains the structural motif that the group of hydroxyl is formed, wherein hydrolyzable obtains the group of hydroxyl, can be selected from halogen, cyano, Oxygen cyano, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketoxime base, alkoxide group.
As an example, suitable silicone hydroxyl primitive includes but not limited to：
Wherein, x is a fixed value or average value, and x is the integer more than or equal to 1；It is preferred that being reacted with other above-mentioned Property group be connected, convenient for by common covalent bond access hydridization dynamic aggregation object, or be connected with connection structure G, formation contains There are two or two or more described in silicone hydroxyl primitive silicone hydroxyl primitive class raw material.Wherein, the connection structure G determines Justice, range of choice, preferred scope are same as above.
As an example, suitable silicone hydroxyl primitive class raw material includes but not limited to：
Wherein x, y, z is the quantity of repetitive unit, can be fixed value or average value, for the integer more than or equal to 1.
In embodiments of the present invention, in addition to above-mentioned generation and/or introducing the necessary raw material of boracic dynamic covalent bond, may be used also Selectively suitably to carry the compound and/or polymer of other reactive groups using arbitrary other.
In embodiment of the present invention, the preparation of the hydridization dynamic aggregation object can be arbitrary conjunction in technological principle Suitable means.It is general that there are two types of modes：Using or first synthesize organic and inorganic boronate primitive class raw material, then with suitable list Hydrocarbon hydroxyl primitive class raw material, dihydroxy primitive class raw material, silicone hydroxyl primitive class raw material reaction, i.e., Macroscopic single crystal last Step generates required boracic dynamic covalent bond, obtains the hydridization dynamic aggregation object of the present invention；Alternatively, using or first synthesis have The raw material of machine boric acid ester bond and/or inorganic borate key and other reactive groups, then by between other reactive groups Reaction, i.e., first prepare required boracic dynamic covalent bond, then completes other reaction steps and obtain the hydridization dynamic aggregation of the present invention Object.
Wherein, the raw material containing boracic dynamic covalent bond can directly select commercially available product, can also be by any appropriate reaction It generates.As an example, suitable reaction is included but are not limited to Types Below：The hydroboration of alkenyl, the oxidation of boron alkyl, Priming reaction between reduction reaction, diboride and alkyl, alkenyl, alkyl halide, amine, ether, the boron of beta-unsaturated carbonyl compounds Change reaction, lithium alkylide, alkyl magnesium are reacted with borate, halogenated boron, boric acid, borax, boric anhydride, borate etc. and alcohol, phenol, silicon The reaction of alcohol, halogenated silanes, the conversion reaction etc. between ester exchange reaction and other kinds end group.The generation of each raw material can be with There are one or more reaction type, reaction means.
Wherein, common covalent bond can be obtained by the reaction by such as following form in other reactive groups：Pass through compound In the amino that contains and the carboxyl contained in compound carry out condensation reaction and form amido bond；Pass through the epoxy contained in compound Amino, the sulfydryl contained in group and compound carries out ring-opening reaction and forms secondary amine key, thioether bond；Initiator or it is outer plus can Under effect, free radical polymerization is carried out by the alkylene contained in compound；Under the action of initiator or outer plus energy, passing through It closes the alkylene contained in object and carries out anion/cation polymerization；By containing in the isocyanate group and compound that contain in compound Some amino, hydroxyl, sulfydryl carry out reaction and form urea bond, urethane bond and thiocarbamate key；Pass through compound In the epoxy group that contains carry out ring-opening polymerisation and form ehter bond；Under monovalence copper catalysis, pass through the azido contained in compound The alkynyl contained in group and compound carries out CuAAC reactions；Pass through the alkene contained in the sulfydryl and compound that contain in compound Alkyl carries out thiol-ene click-reactions；Pass through the addition reaction etc. between the double bond that contains in compound；Wherein, preferably can The mode of enough fast reactions at not higher than 100 DEG C is more preferably capable of the mode of fast reaction at room temperature, including but not limited to Isocyanate group and amino, hydroxyl, the reacting of sulfydryl, acrylate reactions, thiol-ene click-reactions.
In the present invention, since the preparation process step for preparing hydridization dynamic aggregation object using above two embodiment is simple Single, operation is easy, and controllability is strong, therefore is the preferred embodiment of the present invention.But the hydridization dynamic aggregation object in the present invention is not It is only limitted to be prepared using above-mentioned embodiment, can also be between the above embodiment or itself and other kind of embodiment party The combination of formula.
Also include boric anhydride dynamic covalent bond, i.e. organic boron in embodiments of the present invention, preferably in hydridization dynamic aggregation object Acid anhydride key, Inorganic Boron acid anhydride key, organic and inorganic boric anhydride key any one or more of.Although boric anhydride dynamic covalent bond is not the present invention Necessary to inhaling applicable hydridization dynamic aggregation object, but they can selectively be deposited as a kind of control measures Further enriching the performance of material.
In embodiments of the present invention, boric anhydride dynamic covalent bond existing for the selectivity is in polymer molecule Position does not have any restriction, can be located at polymer molecule arbitrary position on, as main chain backbone, side chain skeleton, side group and/or End group is preferably placed at polymer chain skeleton.The content of boric anhydride dynamic covalent bond existing for the selectivity does not have any restriction, Preferably more than the 50% of boracic dynamic key total amount.
In embodiments of the present invention, organic boron acid anhydride key existing for the selectivity may be selected from but not limited to as follows Structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom.
In embodiments of the present invention, Inorganic Boron acid anhydride key existing for the selectivity may be selected from but not limited to as follows Structure：
Wherein, each boron atom is not connected directly with any carbon atom in the structure, and four Z are respectively independent, is determined Justice, range of choice and preferred scope are same as above.Each boron atom can form one, two or three Inorganic Boron in the structure Acid anhydride key, different Inorganic Boron acid anhydride keys can connect cyclization.
In embodiments of the present invention, organic and inorganic boric anhydride key, may be selected from but not limited to existing for the selectivity Such as lower structure：
Wherein, one of boron atom is connected directly at least one carbon atom by boron carbon key in the structure, and extremely A few organic group is connected by the boron carbon key of formation with boron atom；Another boron atom is not former with any carbon in the structure Son is connected directly.
In embodiments of the present invention, the boracic dynamic covalent bond can also be in the form of Macintosh and exist, As an example, it can have the following structure, however, the present invention is not limited thereto：
In embodiments of the present invention, property is also an option that in the hydridization dynamic aggregation object there are dynamic oversubscription Sub- hydrogen bond, the supermolecule hydrogen bond are interacted by one or more kinds of hydrogen bond groups.The hydrogen bond group Can be only present in covalent cross-linking polymer cross-linked network and/or side chain skeletal chain in and non-covalent polymer master In chain and/or side chain skeletal chain (referred to as " skeleton hydrogen bond group ")；It can be only present in the cross-linked network of covalent cross-linking polymer (it is referred to as " pendant hydrogen in the side group of network and/or side chain and in the side group of the main chain of non-covalent polymer and/or side chain Key group "), it can also exist only on polymer chain/small molecule additive end group (referred to as " end group hydrogen bond group "), may be used also To exist simultaneously the hydrogen bond group in above-mentioned any two or two or more positions.When existing simultaneously two or more position Hydrogen bond group when, under specific circumstances, the hydrogen bond group between different location can also form hydrogen bond.The supermolecule hydrogen Key effect can be used as ring formation presence namely hydrogen bond in supermolecule polymerization and/or crosslinking and/or chain that can only play connection Two or more chain segment units, which play, to be increased polymer chain dimensions but does not play supermolecule crosslinked action or hydrogen bond only plays Interchain supermolecule is crosslinked, or only plays in chain two or more arbitrary combination in ring formation or three of the above.
In the present invention, when supermolecule hydrogen bond group forms supermolecule cross-linked network, supermolecule hydrogen bond action therein There can be any appropriate degree of cross linking, (gel point can be contained) more than its gel point, i.e., all polymer molecules are all logical It crosses supermolecule hydrogen bond and is connected with each other and reach the reflecting point of a three-dimensional infinite network for the first time, it can also be below its gel point.If Non-specifically illustrate, in the present invention, for hydrogen bond action, crosslinking refers in particular to the degree of cross linking and (contains gel point) more than gel point；And When the degree of cross linking is zero and other gel points numerical value below, it is accordingly to be regarded as non-crosslinked.
In embodiments of the present invention, the number of teeth of hydrogen bond is not limited.Since the number of teeth of hydrogen bond is more, synergistic effect Bigger, the intensity of hydrogen bond is bigger, if the more intensity of the number of teeth of hydrogen bond are big, the dynamic of hydrogen bond action is with regard to weak, as super Be conducive to play when molecule cross-link and promote hydridization dynamic aggregation object to keep balanced structure and improve mechanical property (modulus and intensity) Effect.If it is low that the number of teeth of hydrogen bond lacks intensity, the dynamic of hydrogen bond action can be carried with regard to strong together with boracic dynamic covalent bond For dynamic property, such as self-repairability, energy absorption characteristics.
In embodiments of the present invention, hydrogen bond group have structure diversity, including but not limited to hydrogen bond donor and by Body number, group size, the length linked and rigidity between polymer chain, the number of the hydrogen bond group connected on polymer chain Amount, can obtain intensity, dynamic, response, crosslink density adjustable hydrogen bond crosslinks on a large scale, at the same by pair and polymer The regulation and control of chain link, can control the dynamic of hydrogen bond, glass transition temperature of cross-linked polymer etc., and then effectively regulate and control Every dynamic property of hydridization dynamic aggregation object.
In embodiments of the present invention, the hydrogen bond group that the hydridization dynamic aggregation object carries can only contain hydrogen bond The hydrogen bond group of donor can also be the only hydrogen bond group containing hydrogen bond receptor, can also be to contain hydrogen bond donor and hydrogen simultaneously The hydrogen bond group of key receptor.When individual hydrogen bond group by only containing hydrogen bond donor or hydrogen bond receptor in the form of in the presence of, simultaneously Must contain in corresponding hydrogen bond receptor or hydrogen-bond donor or system must have other additives to contain corresponding hydrogen bond receptor Or hydrogen-bond donor, to form hydrogen bond.The hydrogen bond donor is exactly hydrogen atom (H), and the hydrogen bond receptor is exactly to receive hydrogen atom Electronegative atom, including but not limited to oxygen atom (O), nitrogen-atoms (N), sulphur atom (S), fluorine atom (F) etc..Such atom can be with Exist with suitable valence state in group.In embodiments of the present invention, the supermolecule hydrogen bond action can be by arbitrary Existing noncovalent interaction generates between suitable hydrogen bond group.In order to be effectively formed hydrogen bond, preferably contain hydrogen simultaneously The hydrogen bond group of key donor and hydrogen bond receptor, as amide groups, carbamate groups, urea groups, thiocarbamate base, imidazoles, The derivative etc. of nitrogen azoles and the above group, at least one of further preferably following constituent：
In embodiments of the present invention, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this)：
In embodiments of the present invention, suitable side group hydrogen bond group and end group hydrogen bond group are except can have above-mentioned skeleton Outside hydrogen bond group structure, more specifically citing such as (but the present invention is not limited only to this)：
Wherein, m, n are the quantity of repetitive unit, can be fixed value can also be average value, preferably smaller than 20, more preferably Less than 5.
In embodiments of the present invention, the generation or introducing of hydrogen bond group may be used any appropriate reaction, including but It is not limited only to Types Below：Isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, succinimide ester groups and amino, Reaction between hydroxyl, sulfydryl, active ester and amino, hydroxyl, sulfydryl react, acyl halide group and amino, hydroxyl, sulfydryl it is anti- It answers, anhydride group and amino, hydroxyl, sulfydryl react, and epoxy and amino, hydroxyl, sulfydryl react, the reaction of urea-amine, acyl Aminating reaction, free radical acrylate reaction, double bond radical reaction, double bond cyclization, nitrine-alkynes click-reaction, sulfydryl- Double bond/alkynes click-reaction, tetrazine-norbornene reaction, silicone hydroxyl condensation reaction；Preferred isocyanate and amino, hydroxyl, sulfydryl Reaction, the reaction of urea-amine, active ester and amino, hydroxyl, sulfydryl react；More preferable isocyanates and amino, hydroxyl, The reaction of sulfydryl.The generation or introducing of hydrogen bond group can there are one or more reaction type, reaction means, the oversubscription of formation Son crosslinking can there are one or more type, structure.
In embodiments of the present invention, the hydridization dynamic aggregation object is more preferably simultaneously comprising at least one organic boron Acid esters key, at least one inorganic borate key, at least one supermolecule hydrogen bond and at least one boric anhydride dynamic covalent bond.
The present invention also provides a kind of hydridization dynamic aggregation object, the hydridization dynamic aggregation object contains following borate simultaneously Dynamic covalently at least one of key combination：The combination of organic boronic monoester bond and Inorganic Boron acid monoester key, organic boronic monoesters The combination of key and inorganic boric acid cyclic ester key, the combination of organic boronic monoester bond and inorganic boric acid estersil key, organic boronic cyclic ester key With the combination of Inorganic Boron acid monoester key, the combination of organic boronic cyclic ester key and inorganic boric acid cyclic ester key, organic boronic cyclic ester key and The combination of inorganic boric acid estersil key, the combination of organic boronic estersil key and Inorganic Boron acid monoester key, organic boronic estersil key and nothing The combination of machine boric acid cyclic ester key.Wherein, including borate dynamic covalent bond be hydridization dynamic aggregation object molecule aggregation or poly- It closes and crosslinked tie point.Wherein, the preferably described hydridization dynamic aggregation object also contains at least one boric anhydride dynamic covalent bond.
The present invention also provides a kind of hydridization dynamic aggregation object, the hydridization dynamic aggregation object has containing at least one simultaneously Machine boric acid ester bond and at least one inorganic borate key, and contain supermolecule hydrogen bond simultaneously；Organic boric acid ester included in it Key and inorganic borate key are hydridization dynamic aggregation object molecule aggregation or polymerization and crosslinked tie point；The wherein organic boron Acid esters key contains at least one comprising structure shown in preceding formula (1), and the inorganic borate key contains before at least one includes Structure shown in formula (2).Wherein, including borate dynamic covalent bond be hydridization dynamic aggregation object molecule aggregation or polymerization and Crosslinked tie point.Wherein, the dynamic supermolecule hydrogen bond is by the hydrogen bond group simultaneously containing hydrogen bond donor and hydrogen bond receptor It interacts, preferably at least one hydrogen bond group phase by containing the constituent as shown in preceding formula (14A) and formula (14B) Interaction forms；Wherein, the more preferably described hydridization dynamic aggregation object also contains at least one boric anhydride dynamic covalent bond.
In every case in embodiments using above-mentioned all kinds of raw materials as raw material carry out preparation hydridization dynamic aggregation object, no matter its It is in the form of raw material, also or is intermediate product with synthetic polymer or in the form of the compound of synthesis material Form ought to be included in the scope of patent protection of the present invention since it according to the present invention can instruct to be obtained.Equally Ground, those skilled in the art according to the present invention can also instruct, and reasonably implement to obtain institute using above-mentioned several compounds The hydridization dynamic aggregation object stated.
In embodiments of the present invention, the hydridization dynamic aggregation object has one or more glass transition temperatures Degree, preferably at least there are one glass transition temperatures to be not higher than 25 DEG C, and more preferable each glass transition temperature is not higher than 25 ℃.The system that each glass transition temperature is not higher than 25 DEG C is good flexible and flowable due to having at a temperature of routine use Property/creep properties, therefore used particularly suitable as defense of resistance to impact material.The vitrifying of hydridization dynamic aggregation object is turned Temperature can be measured by the assay method of general glass transition temperature in this fields such as DSC, DMA.
The heteroatom group being previously mentioned in the present invention can be any appropriate containing heteroatomic group, can Selected from following any group, but the present invention is not limited only to this：Halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine groups, silicon substrate, phosphorus It is base, triazole, isoxazoles, amide groups, imide, thioamides base, enamine base, carbonate group, carbamate groups, thio Carbamate groups, thioester substrate, ortho acid ester group, phosphate-based, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate group, phosphoryl, Phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphoryl, carbamide, phosphamide, phosphorous acyl Amine, pyrophosphoramide, cyclophosphamide, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, diazanyl, hydrazide group, thio phosphinylidyne It is diazanyl, azo carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, thiocarbazates base, carbonohydrazides, thio Carbonohydrazides, azo group, urea groups, isourea base, isothiourea group, allophanate group, thioallophanate base, guanidine radicals, amidino groups, amino Guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonate group, sulfinic acid ester Base, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide, triazoline diketone.
The molecular weight being previously mentioned in the present invention is no more than the small molecule alkyl of 1000Da, typically contains 1 to 71 carbon Atom can contain heteroatom group, and can be free of has heteroatom group.Generally, the small molecule alkyl can be selected from By it is any in the following group, any it is unsaturated in the form of, it is any substituted form, any by hydridization form and its group It closes：C1-71Alkyl, ring C3-71Alkyl, phenyl, benzyl, aryl；Small molecule alkyl is preferably methyl, ethyl, propyl, propylene, fourth Base, butylene, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl；More preferably methyl, ethyl, propyl, benzene Base.
The molecular weight being previously mentioned in the present invention is more than the polymer chain residue of 1000Da, can be any appropriate polymerization Object chain residue includes but are not limited to carbochain polymer residue, heterochain polymer residue, elemento-organic polymer residue.Wherein, Polymer can be homopolymer, or appoint the copolymer of several monomers, oligomer or polymer composition；Polymer chain can be flexibility Chain or rigid chain.
Wherein, the carbochain polymer residue can be any appropriate macromolecular main chain mainly by carbon atom structure At polymer residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form, It is any by hydridization form and combinations thereof：Polyolefins chain residue, such as Polyethylene Chain residue, polypropylene chains residue, poly- isobutyl Alkene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain residue, polytetrafluoroethylene (PTFE) chain residue, poly- three Fluorine vinyl chloride chain residue, polyvinyl acetate chain residue, Polyvinylalkylethers chain residue, polybutadiene chain residue, poly- isoamyl Diene chain residue, polychlorobutadiene chain residue, polynorbornene chain residue etc.；Polyacrylic chain residue, such as polyacrylic acid chain Residue, polyacrylamide chain residue, polymethyl acrylate chain residue, polymethyl methacrylate chain residue etc.；Polypropylene nitrile Chain residue, such as polyacrylonitrile chain residue；It is preferred that Polyethylene Chain residue, polypropylene chains residue, polyvinyl chloride chain residue, polybutadiene Alkene chain residue, polyisoprene chain residue, polyacrylic acid chain residue, polyacrylamide chain residue, polyacrylonitrile chain residue.
The heterochain polymer residue, can be any appropriate macromolecular main chain mainly by carbon atom and nitrogen, oxygen, The polymer residue that the hetero atoms such as sulphur are constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, it is any It is substituted form, any by hydridization form and combinations thereof：Polyethers chain residue, such as polyethylene oxide chain residue, polycyclic oxygen Propane chain residue, PolyTHF chain residue, asphalt mixtures modified by epoxy resin fat chain residue, phenolic resin chain residue etc.；Polyesters chain residue, it is such as poly- Caprolactone chain residue, poly- valerolactone chain residue, polylactide chain residue, unsaturated polyester (UP) chain residue, alkyd resin chain residue, life Object polyester chain residue etc.；Polyamine class chain residue, such as polyamide chains residue, polyimides chain residue, polyurethane chain residue, polyureas chain Residue, Lauxite chain residue, melamine resin chain residue etc.；Polysulfide heterochain residue, such as polysulfones chain residue；It is preferred that polycyclic oxygen second Alkane chain residue, PolyTHF chain residue, asphalt mixtures modified by epoxy resin fat chain residue, polycaprolactone chain residue, polylactide chain residue, polyamide Chain residue, polyurethane chain residue, polyureas chain residue；The heterochain polymer residue can pass through click-reaction, such as CuAAC Reaction, thiol-ene react to be formed.
The elemento-organic polymer residue can be any appropriate macromolecular main chain mainly by silicon, boron, aluminium etc. The hetero atoms such as inorganic elements hetero atom and nitrogen, oxygen, sulphur, phosphorus constitute polymer residue, can be selected from it is any in the following group, appoint It is a kind of unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silicone-based polymers Chain residue, such as poly-organosilicon alkane chain residue, polysiloxane chain residue, poly-organosilicon borine chain residue, poly-organosilicon azane Chain residue, poly-organosilicon sulfane chain residue, poly- organophosphor siloxane chain residue, poly- organic metal siloxane chain residue；Organic boron Type of Collective object chain residue, such as poly- organo-borane chain residue, poly- organic boron sulfane chain residue, poly- have poly- organic boron azane chain residue Machine boron phosphine chain residue etc.；Organic phosphates polymer chain residue；Organic leadP Type of Collective object chain residue；Organic tin polymer chain is residual Base；Organo-arsenic Type of Collective object chain residue；Antimony organic Type of Collective object chain residue；It is preferred that poly-organosilicon alkane chain residue, poly organo Alkane chain residue, poly- organo-borane chain residue.
The molecular weight being previously mentioned in the present invention is no more than the inorganic molecules chain residue of 1000Da, can be arbitrary conjunction What suitable molecular backbone and side chain was mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic molecules chain residue, generally, the inorganic molecules chain residue can be selected from any in the following group, any It is unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silane (silicon-carbon) chain residue, silicon Oxygen compound chain residue, sulphur silicon compound chain residue, sulfur-nitrogen compound chain residue, phosphazene compound chain residue, phosphoric-oxygenic compound Chain residue, borine chain residue, silazane chain residue residue；It is preferred that silane chain residue, silicon oxide compound chain residue, phosphazene compound Chain residue, borine chain residue.
The molecular weight being previously mentioned in the present invention is more than the inorganic macromolecular chain residue of 1000Da, can be any appropriate Macromolecular main chain and side chain be mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic macromolecular chain residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted shape It is formula, any by hydridization form and combinations thereof：Polysilane chain residue, polysiloxane chain residue, polysulfide silicon chain residue, polysulfide nitrogen Chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene are for phosphonitrile chain residue, polyborane chain residue；Also selected from the following group In any inorganic macromolecular with residue or any inorganic macromolecular with residue being modified by surface：Zeolite type Molecular sieve, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecular sieve, diamond, graphite, graphene, graphite oxide Alkene, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, silica, silicon disulfide, silicon nitride, Silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, nitridation sulphur, silicon Change calcium, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, water aluminium Stone, gibbsite, corundum, titanium dioxide；It is preferred that polysilane chain residue, polysiloxane chain residue, polyphosphazene chain residue, polyborane chain Residue, by surface be modified graphene, by surface be modified carbon nanotube, by surface be modified carbon fiber, by table The silica of face modification, the silicon nitride being modified by surface, the silicon carbide being modified by surface, the silicic acid being modified by surface Salt, the glass fibre being modified by surface, the boron nitride being modified by surface.
For small molecule alkyl, polymer chain residue, inorganic molecules chain residue, inorganic macromolecular chain residue structure simultaneously Be not particularly limited, can be straight chain type, branched chain type, star-like, H-type, combed, dendritic, mononuclear type, polycyclic type, loop coil type, Condensed ring type, bridged ring type, the chain with cyclic structure, two and three dimensions cluster type and combinations thereof；In small molecule alkyl, polymer chain In residue, inorganic molecules chain residue, inorganic macromolecular chain residue, soft segment can be contained, can also contain rigid chain segment, Flexible and rigid chain segment can be contained simultaneously, preferably based on soft segment.
The suitable polymerization being previously mentioned in embodiments of the present invention can appoint by the way that this field is general A kind of suitable polymerisation carries out, and it is anti-to include but are not limited to condensation polymerization reaction, polyaddition reaction, ring-opening polymerisation It answers；Wherein, it is anti-to include but are not limited to Raolical polymerizable, anionic polymerisation, cationic polymerization for polyaddition reaction It answers, coordination poly-merization.
In specific implementation process, raw materials of compound can utilize above-mentioned any polymerisation process, pass through this field General any suitable polymerization technique implement.For example, when raw materials of compound obtains hydridization in the form of condensation polymerization When dynamic aggregation object, it can be implemented by polymerization techniques such as melt polymerization, polymerisation in solution, interfacial polymerizations；In another example working as When conjunction raw material obtains hydridization dynamic aggregation object in the form of free radical polymerization, bulk polymerization, polymerisation in solution, suspension can be passed through The polymerization techniques such as polymerization, emulsion polymerization are implemented；For another example being moved when raw materials of compound obtains hydridization in the form of ionic polymerization When state polymer, it can be implemented by polymerization techniques such as polymerisation in solution, slurry polymerization, gas-phase polymerizations.Above-mentioned each polymerization side Method is well known to those skilled in the art and widely used polymerization, can be adjusted according to actual conditions, here No longer it is developed in details.
In each preparation embodiment of the present invention, it can be incited somebody to action by any appropriate material hybrid mode known in the art The raw material centainly matched can be interval, semicontinuous or continuous processing form by being mixed with hydridization dynamic aggregation object Mixing；Similarly, interval also may be selected, semicontinuous or continuous processing form is molded hydridization dynamic aggregation object.It uses Hybrid mode include but are not limited to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling Deng wherein it is preferred that solution is stirred, melts and be stirred and melting extrusion.Energy in material mixed process provides form Include but are not limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use include but are not limited to extrusion molding, Injection moulding, compression molding, tape casting, calendering formation, cast molding.
In the preparation process of hydridization dynamic aggregation object, after the compound as raw material mutually participates in reaction, raw material group / can be polymerize as linking point using boracic dynamic covalent bond or common covalent bond, obtain that there is the miscellaneous of higher molecular weight Change dynamic aggregation object.Prepare the various raw materials selected by hydridization dynamic aggregation object can flexible handle at component selections and formula rate It holds, but should be closed according to target material performance and the structure of selected compounds, the reactive group number contained and molecular weight The design and combination of reason.The various raw material components added should ensure that functional group and/or other reactivity in reactant system The molar equivalent ratio of group is in range appropriate.The functional group contained in raw material components can react completely, can also part Reaction, but be not required for wherein all groups and be involved in reaction, only chemical bond to be formed is enough to maintain hydridization dynamic aggregation Object structure.Wherein, work as with/without the sum of machine boric acid primitive functional group and the sum mole of hydroxyl primitive functional group in raw material Range of the amount than preferably 0.1~10, more preferable 0.3~3 range, more preferable 0.8~1.2 range.When in raw material with/without machine The molar equivalent ratio of the sum of boric acid primitive functional group's sum and hydroxyl primitive functional group is close to 1:When 1, reaction interval can be obtained The hydridization dynamic aggregation object that degree is high, stability is good；When the sum and hydroxyl base with/without machine boric acid primitive functional group in each raw material The molar equivalent of the sum of first functional group is than deviateing 1:When 1, then the preferable hydridization dynamic aggregation object of dynamic can be obtained.Equally Ground, when selecting other raw materials to participate in preparing hydridization dynamic aggregation object as reactive component, other reactivity in reactant system The molar equivalent of group carries out the molar equivalent of other reactive groups of polymerisation than excellent than also should be at range appropriate Select 0.1~10 range, more preferable 0.3~3 range, more preferable 0.8~1.2 range.In actual fabrication process, ability The technical staff in domain can be adjusted according to actual needs.
During preparing the hydridization dynamic aggregation object containing boracic dynamic covalent bond using all kinds of raw materials in the present invention, It, can be according to needing the strand of the functional group of different number, different structure by the design and adjustment to compound structure The organic structures such as section, the molecule segment of different molecular weight, reactive group, functional groups are introduced into raw materials of compound, and The structural constituent for becoming hydridization dynamic aggregation object by preparation process, to be realized to hydridization dynamic aggregation object in wide range The regulation and control of structure.The diversity of hydridization dynamic aggregation object structure, but also it embodies abundant different performance, and can be according to poly- It closes performance possessed by object and is applied to different fields.What is more important, those skilled in the art often also can roots According to the needs of practical application, the structure and performance of polymer are designed from source；During this, used organic knot Technical staff's regulation and control can be become if structure (such as organic boron structure, organosilicon structures, polyol structure) and design hydridization dynamic and gathered Close effective medium of object structure.
Wherein, it by the design to structure of functional groups in each raw material, can prepare active miscellaneous with Different Dynamic Change dynamic aggregation object.For example, being connected with phenyl boric acid/borate ester structure of aminomethyl using ortho position or ortho position is connected with amide groups Phenyl boric acid/borate ester structure prepares hydridization dynamic aggregation object, and the aminomethyl or amide groups at ortho position can play promotion dynamic Effect；For another example after being connected with strong electron-withdrawing group (such as fluorine atom, acetate, pyridyl group, piperidyl) in boron atom, The reaction rate of itself and hydroxyl also greatly improves；Thus obtained hydridization dynamic aggregation object can embody higher dynamic and live Property so that the boracic dynamic covalent bond in polymer can show dynamic reversibility under conditions of more mild, but also Hydridization dynamic aggregation object can be prepared and be used under conditions of more mild, and the application range of polymer is extended.
It, can also be by way of introducing functional groups in each raw material in the preparation process of hydridization dynamic aggregation object The performance of hydridization dynamic aggregation object is regulated and controled.For example, improving hydridization dynamic aggregation object by introducing hydrophobic group Hydrolytic resistance；The fluorescent hydridization dynamic aggregation object of tool is prepared by introducing fluorophor；By introducing antioxidant groups To improve the inoxidizability of hydridization dynamic aggregation object；Hydridization dynamic aggregation object is moved by introducing acidic-group or basic group State property is adjusted.In another example when needing hydridization dynamic aggregation object being blended with other polymers, it can also be by drawing Enter the structural constituent or coupling group similar with other polymers, to achieve the purpose that improve compatibility between component.
In the preparation process of hydridization dynamic aggregation object, by regulating and controlling functional group number or other reactivity in each raw material Group number can be prepared with line style, ring-type, branched or cross-linked structure hydridization dynamic aggregation object.
In addition, in embodiments of the present invention, the form of the hydridization dynamic aggregation object can be solution, lotion, Cream, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), Ordinary solid, elastomer, foamed material etc..Ordinary solid because also most easy with better mechanical property, preparation method, because This is more preferred.Elastomer and its foam also have good mechanical property while with more preferably energy-absorbing effect, therefore more It is preferred that.
In the preparation process of hydridization dynamic aggregation object, mainly using mechanical foaming method, physical blowing method, chemical blowing The methods of method, emulsion template foaming, freeze-drying foaming foam to hydridization dynamic aggregation object.Above-mentioned foaming method is equal Known technological means is disclosed for this field, and those skilled in the art can prepare situation and target polymerization physical property according to practical Suitable foaming method and foamed material forming method can be selected to prepare hydridization dynamic aggregation object foamed material.
All moved to hydridization to what the compound component structure as raw material in the present invention can play as previously discussed The some examples explanations of state polymer performance regulation and control sets hydridization dynamic aggregation object properity in the present invention, purposes Meter, adjustable extent is extensive, and many unexpected actual effects are reflected toward contact, it is difficult to accomplish exhaustion, this field Technical staff can be adjusted with thinking according to the present invention.
It, can also be according to feelings in the range of not interfering the object of the invention in the preparation process of hydridization dynamic aggregation object Condition selection be added or used to other polymers, auxiliary agent, filler collectively as hydridization dynamic aggregation object recipe ingredient, or miscellaneous Change and plays the role of improving processing performance in the preparation process of dynamic aggregation object.
Wherein, the other polymers, can be played in system improve material property, assign material new capability, It improves materials'use and economic benefit, have the function that material comprehensively utilizes.Addible other polymers can be selected from natural High-molecular compound, synthetic resin, synthetic rubber, synthetic fibers.The present invention is to the character of polymer added and is had Some molecular weight do not limit, and can be oligomer or high polymer according to the difference of molecular weight, not according to polymeric species Together, it can be homopolymer or copolymer, should prepare in the specific use process according to the performance of target material and actually The needs of journey and selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound：Natural rubber, chitosan, chitin, native protein etc..
When the other polymers are selected from synthetic resin, it can be selected from following any or appoint several synthetic resin： Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), makrolon, Dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, Polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact poly Styrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl Ester copolymer, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-acetic acid Vinyl ester copolymers, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP) etc..
When the other polymers are selected from synthetic rubber, it can be selected from following any or appoint several synthetic rubber： Isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorubber, Lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc..
When the other polymers are selected from synthetic fibers, it can be selected from following any or appoint several synthetic fibers： Viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polyester fiber, polyurethane fiber, polypropylene Nitrile fiber, polyvinyl chloride fibre, polyolefine fiber, fluorofibre etc..
In the preparation process of polymer material, the preferred natural rubber of the other polymers, polyethylene, polypropylene, Vinyl-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, asphalt mixtures modified by epoxy resin Fat, phenolic resin, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon Rubber, polyurethane rubber, thermoplastic elastomer (TPE).
Wherein, the auxiliary agent may include but be not limited to the combination of following one or more, such as additive synthesis, including catalysis Agent, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer, dispersant, emulsifier, fire retardant；Improve The auxiliary agent of mechanical property, including chain extender, toughener, coupling agent, crosslinking agent, curing agent；The auxiliary agent of processing performance is improved, including Solvent, lubricant, releasing agent, plasticizer, thickener, thixotropic agent, levelling agent；Change the auxiliary agent of coloured light, including colorant, fluorescence Brightening agent, delustering agent；Other auxiliary agents, including antistatic agent, biocide mildewcide, foaming agent, nucleating agent, rheological agent, dynamic regulation Agent etc..
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.It includes but are not limited to following any or appoints several catalyst：1. polyurethane closes At with catalyst：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- dimethylaminos- Ethyoxyl) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) two Isopropanolamine, N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyleyelohexanes Amine, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethyl ethanols Amine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls caproic acid, N, N- dimethyl benzylamines, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, dioctyl tin two Laurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, phenylmercuric acetate, propionic acid Benzene mercury, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；2. polyolefin catalyst for synthesizing：Such as Zi egler- Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, titanium tetrachloride, tri-chlorination Titanium, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter Ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc.；3. CuAAC catalysts：By monovalence Copper compound and amine ligand share concerted catalysis；Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine Ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), three [(1- tertiary butyls -1H-1,2,3- Triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；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 0.01-0.5wt%.
Initiator in the auxiliary agent can cause monomer molecule to activate in polymerization process and generate free Base improves reaction rate, and reaction is promoted to carry out, and includes but are not limited to following any or appoints several initiators：1. free radical Polymerization initiator：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), dicetyl peroxydicarbonate diisopropyl Bis- (4- tert-butylcyclohexyls) esters of ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tert-butyl hydroperoxide benzoic acid Ester, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azo two Isobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization causes Agent：Such as 2,2,6,6- tetramethyls -1- oxygroups piperidines, 1- chloro-1-phenyls ethane/stannous chloride/bis- pyridines ternary system；3. from Sub- polymerization initiator：Such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, butter of tin/alkyl halide system；4. matching Position polymerization initiator：Such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；5. ring-opening polymerisation Use initiator：Such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, the preferred mistake of initiator Aoxidize lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, and one As be 0.1-1wt%.
Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, ensure that material can be suitable Its service life is processed and extended sharply, includes but are not limited to following any or appoints several antioxidant：Hinered phenols, Such as 2,6 di tert butyl 4 methyl phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) butane, four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenols)；Sulfur-bearing by Hinder phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert-butylphenols]； Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization isocyanide Acid esters Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) P-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thiodipropionic acid dilauryl Osmanthus ester, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, three nonyl benzene of phosphorous acid Ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Used Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent can prevent polymer samples from light aging occurs, extend its service life, It includes but are not limited to following any or appoints several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous Sour calcium；Ultra-violet absorber, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyls Base -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzotriazole, (the 2- hydroxyls of 2,4,6- tri- Base -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls；Pioneer's type is ultraviolet Light absorbers, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3,5- bis- tertiary fourths Base -4- benzylphosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer, such as the last of the ten Heavenly stems two Bis- (2,2,6,6- tetramethyl piperidines) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidines) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamates, N, positive fourth positive group aminodithioformic acid nickel of N '-two etc.；Its In, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used is stablized Agent dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent enables to polymer samples during processing or use not due to heated Chemical change occurs, or delays these variations to achieve the purpose that prolong the service life comprising but it is not limited only to following A kind of or several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, stearic acid Lead, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate Mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；It is sub- Phosphoric acid ester, such as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphorous acid Ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer, such as altogether Precipitate metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer etc.；Wherein, the preferred barium stearate of heat stabilizer, Calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not limit especially It is fixed, generally 0.1-0.5wt%.
Dispersant in the auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into tiny particle And be suspended in liquid, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, while can also prevent particle Sedimentation and cohesion, form and stabilize suspension comprising but be not limited only to following any or appoint several dispersants：Anionic, Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as aliphatic alcohol polyethenoxy Ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, such as starch, bright Glue, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonates, polyvinyl alcohol Deng.Wherein, the preferred neopelex of dispersant, naphthalene system methylene sulfonate (dispersant N), aliphatic alcohol polyethenoxy Ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.
Emulsifier in the auxiliary agent can improve in the mixed with polymers liquid comprising auxiliary agent between various composition phases Surface tension is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any or appoint several Kind emulsifier：Anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, Negel, succinic acid Sulfonated ester, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, phosphate ester salt, Fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylate Type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fat Fat acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite And sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferably neopelex, mistake Water Span, triethanolamine stearate (Emulphor FM), emulsifier used are not particularly limited, generally For 1-5wt%.
Fire retardant in the auxiliary agent can increase the flame resistance of material comprising but be not limited only to following any Or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol Ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organohalogen compounds are such as high Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethanes, deca-BDE, penta decane of perchloro- ring；Inorganic combustion inhibitor, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as the anti-butylene of chlorendic anhydride, bis- (2,3- dibromopropyls) two Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.
Chain extender in the auxiliary agent can be such that strand expands with the reaction-ity group reaction on reactant molecule chain Exhibition, molecular weight increase comprising but be not limited only to following any or appoint several chain extenders：Polyalcohols chain extender, such as second two Alcohol, propylene glycol, diglycol, glycerine, trimethylolpropane, pentaerythrite, 1,4- butanediols, 1,6-HD, to benzene Diphenol dihydroxyethyl ether (HQEE), resorcinol double hydroxyethyl ether (HER), to bis-hydroxyethyl bisphenol A；Polynary amine chain extender, Such as diaminotoluene, diamino dimethylbenzene, tetramethyl xylylen diamines, tetraethyl diphenyl methylene diamines, tetra isopropyl Hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminomethyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '- Diphenylmethanediamiand (MOCA), 3,5- dimethythiotoluene diamines (DMTDA), 3,5- diethyl toluene diamines (DETDA), 1, 3,5- triethyl group -2,6- diaminobenzenes (TEMPDA)；Alcamines chain extender, such as triethanolamine, triisopropanolamine, N, the bis- (2- of N '- Hydroxypropyl) aniline.Chain extender dosage used is not particularly limited, generally 1-20wt%.
Toughener in the auxiliary agent can reduce polymer samples brittleness, increase toughness, and it is strong to improve material carrying Degree comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-butadiene-styrene is copolymerized Resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylonitrile-butadiene-benzene second Alkene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-butadiene-benzene Ethylene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), benzene second Alkene-butadiene-styrene block copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS), Chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent can improve the interface characteristics of polymer samples and inorganic filler or reinforcing material Can, the viscosity of material melt is reduced in plastic processes, improves the dispersion degree of filler to improve processing performance, and then make system Product obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any or appoint several couplings Agent：Chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.；Wherein, The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(the third oxygen of 2,3- epoxies) propyl trimethoxy Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
Crosslinking agent in the auxiliary agent, cooperation need to carry out crosslinked reactant composition progress in dynamic aggregation object It uses, bridging action can be played between the polymer molecule of line style, so that multiple linear molecules is mutually bonded and be cross-linked into reticular structure, The crosslink density and cross-link intensity that polymer can be further increased improve the heat resistance and service life of polymer, simultaneously Improve the mechanical performance and weatherability of material comprising but be not limited only to following any or appoint several crosslinking agents：Polypropylene glycol Glycidol ether, zinc oxide, aluminium chloride, aluminum sulfate, chromic nitrate, ethyl orthosilicate, methyl orthosilicate, p-methyl benzenesulfonic acid, to first Benzene sulfonyl chloride, diacrylate -1,4- butanediol esters, ethylene glycol dimethacrylate, butyl acrylate, aluminium isopropoxide, acetic acid Zinc, titanium acetylacetone, aziridine, isocyanates, phenolic resin, hexamethylenetetramine, cumyl peroxide, peroxidating bay Acyl, peroxidating stearoylketene, benzoyl peroxide, cyclohexanone peroxide, benzoyl peroxide ethyl ketone, di-t-butyl peroxide, adjacent benzene mistake Oxygen dicarboxylate, isopropyl benzene hydroperoxide, three tert-butyl peroxy base silane of vinyl ,-two tert-butyl peroxy base silicon of diphenyl Alkane, trimethyl t-butyl peroxy silane etc..Wherein, the preferred cumyl peroxide of crosslinking agent (DCP), benzoyl peroxide (BPO), peroxidating 2,4 dichloro benzene formyl (DCBP).Dosage of crosslinking agent used is not particularly limited, generally 0.1- 5wt%.
Curing agent in the auxiliary agent, cooperation need to carry out cured reactant composition progress in dynamic aggregation object It uses, can promote or control the curing reaction of reactant composition in the course of the polymerization process comprising but be not limited only to following any Kind appoints several curing agent：Amine curing agent, as ethylenediamine, diethylenetriamine, triethylene tetramine, dimethylaminopropylamine, six times Tetramine, m-phenylene diamine (MPD)；Acid anhydride type curing agent, such as phthalic anhydride, maleic anhydride, pyromellitic acid dianhydride；Amide Class curing agent, such as Versamid；Imidazoles, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles；Trifluoro Change boron complex etc..Wherein, the preferred ethylenediamine of curing agent (EDA), diethylenetriamine (DETA), phthalic anhydride, maleic Dicarboxylic anhydride, hardener dose used are not particularly limited, generally 0.5-1wt%.
Solvent in the auxiliary agent can adjust viscosity, be convenient for technological operation, make in product preparation process or in preparing With.It includes but are not limited to following any or appoints several：Hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as dichloromethane, Chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrochysene furan Mutter, dioxane), esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol list first Ether acetate), dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) etc..Solvent dosage used is not particularly limited, Generally 1-200wt%.
Lubricant in the auxiliary agent can improve the lubricity of polymer samples, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid, hydroxy stearic acid；Fat Esters of gallic acid, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type is such as hard Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamides；Fatty alcohol and polynary Alcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate, Zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used Agent dosage is not particularly limited, generally 0.5-1wt%.
Releasing agent in the auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean comprising but It is not limited only to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol Deng；Wherein, the preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5- 2wt%.
Plasticizer in the auxiliary agent can increase the plasticity of polymer samples so that the hardness of polymer, mould Amount, softening temperature and brittle temperature decline, and elongation, flexibility and flexibility improve comprising but be not limited only to following any Kind appoints several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, phthalic acid two Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl Bis- (13) esters of ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthaldehyde Sour two (2- ethyls) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester, such as The own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy fat Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy soybean Oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate, binary Alcohol lipid, such as the sour glycol esters of C5~9, the sour Triethylene Glycols of C5~9；Class containing chlorine such as afforests paraffin class, chlorinated fatty acid Ester；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, trimellitic acid Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), neighbour Dibatyl phithalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene two Formic acid diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Thickener in the auxiliary agent, can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, and one As the present invention production and semi-finished product storage during use comprising but be not limited only to it is following any or appoint several thickenings Agent：Lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulfate, alkyldimethylamine oxide, aliphatic acid monoethanol Amide, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut monoethanolamide Propyl betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazoles quinoline, titanate coupling agent；Polymer substance, such as bentonite, manually Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch, Seaweed acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide, Polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc.；Wherein, the preferred hydroxy ethyl fiber of thickener Element, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally For 0.1-1.5wt%.
Thixotropic agent in the auxiliary agent is added in hydridization dynamic polymer systems, increases the thixotropy of polymeric system. It includes but are not limited to following any or appoints several：Gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silicic acid derive Object, urea derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt%.
Levelling agent in the auxiliary agent can ensure that the flat smooth of polymer coating film is uniform, improve film coated surface matter Amount improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Dimethyl silicone polymer, poly- methyl Phenyl siloxane, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, the preferred poly dimethyl of levelling agent Siloxanes, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
Colorant in the auxiliary agent can make polymeric articles show required color, increase surface color and polish, It includes but are not limited to following any or appoints several colorants：Inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium Red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang The bright red R of red HF3C, the plastics and not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, Phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rose Rare essence, Oil Yellow etc.；Wherein, the selection of colorant need not be particularly limited to depending on color sample demand.Coloring used Agent dosage is not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent can make contaminated substance obtain the sparkling effect of similar fluorite, It includes but are not limited to following any or appoints several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline type, benzo Oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent CBS), bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene) Dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.
Delustering agent in the auxiliary agent when incident light being enabled to reach polymer surfaces, occurs diffusing reflection, generates low The matt and delustring appearance of gloss comprising but be not limited only to following any or appoint several delustering agents：Settle barium sulfate, dioxy SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred silica of delustering agent.Used disappears Photo etching dosage is not particularly limited, generally 2-5wt%.
The deleterious charge assembled in polymer samples can be guided or eliminated, makes it by the antistatic agent in the auxiliary agent Not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several antistatic agents：The moon from Subtype antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, alkyl phenol Polyoxyethylene groups ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, alkyl polyoxyethylene base ether sulfonic acid triethanolamine, phosphoric acid Bis- [two (2- the ethylol amines)] phosphates of ester derivant, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl, phosphate Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, N, N- cetyls-ethyl morpholine ethyl-sulfate salt, stearamide propyl (2- hydroxyl second Base) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2- alkyl -3,3- dihydroxy ethyl imidazolines perchlorate, 2- Heptadecyl -3- ethoxy -4- carboxymethyls imidazoline, N, bis- (α-ethoxy)-N-3 (dodecyloxy -2- hydroxypropyls) first of N- Ammonium Methylsulfate salt；Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- tri- Alkylammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N- lauryls-N, N-, alkyl two Salt hydroxide, -3 ethoxy -3- acetic acid alkali imidazolines quaternary amine alkali of 2- alkyl, N- alkyl amino acids in (polyoxyethylene) ammonium second Salt；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol epoxy second The polyethylene oxide of alkane addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, sorbitan mono-laurate Addition product；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol-terephthalic acid (TPA) such as ethylenediamine Ester -3,5- dibenzoates sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- acetonyl pyrroles Pyridine phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, octadecyldimethyl hydroxyl second Base quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used does not have It is particularly limited to, generally 0.3-3wt%.
Dehydrating agent in the auxiliary agent, moisture that can be in removing system comprising but be not limited only to it is following any or Appoint several：It is oxazolidine compound (such as 3- Ethyl-2-Methyls -2- (3- methyl butyls) -1,3- oxazolidines), different to Methyl benzenesulfonyl Cyanate, triethyl orthoformate, vinyl silanes, calcium oxide etc..Dehydrating agent dosage used is not particularly limited, generally 0.1-2wt%.
Biocide mildewcide in the auxiliary agent can inhibit the growth of bacterium, and the appearance for keeping product clean and tidy extends and uses Service life；Or protection user, the health for promoting user, such as reduce tinea pedis.It includes organic matter and inorganic matter, including but It is not limited only to following any or appoints several：Isothiazolinone derivatives, such as 5-Chloro-2-methyl-4-isothiazolin-3-one, 2- Methyl -4- isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketones, octylisothiazolinone, 2,4,4- tri- Chlorine-2-hydroxyl-diphenyl ether, 2- (4- thiazolyls) benzimidazole, copper 8-quinolinolate or bis- (8-hydroxyquinoline base) copper；It is organic Tin compound, such as tributyl-tin fumarate, tributyltin acetate, bis- (tributyl tin) sulfide, bis- (tributyl tin) tin oxide； N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide；Inorganic compound or compound, such as nano silver, nano-silica Change titanium, nano silicon dioxide, nano zine oxide, superfine cupper powder, inorganic antiseptic YY-Z50, XT inorganic antiseptic, composite antibacterial Agent KHFS-ZN.Biocide mildewcide dosage used is not particularly limited, generally 0.5-2wt%.
Foaming agent in the auxiliary agent, can so that polymer samples foam pore-forming, to obtain light, heat-insulated, sound insulation, Flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Physical blowing agent, such as third Alkane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether, chlorine Methane, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, Ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-dinitroso is to benzene two Formamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, azo two are different Butyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide,-two sulphur of biphenyl -4,4 ' Acyl azide；Foamed promoter, as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, Lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, stearyl chloride, benzene diformazan Acyl chlorides, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, Thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, foaming agent is preferred Sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitros, N, N '- Dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used It is not particularly limited, generally 0.1-30wt%.
Nucleating agent in the auxiliary agent can be accelerated crystalline rate, increase knot by the crystallization behavior of change polymer Brilliant density and promote fine grain size, reach and shorten material molding cycle, improves the product transparency, lustrous surface, tension The purpose of the physical mechanical properties such as intensity, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but be not limited only to Under it is any or appoint several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, silica, two Benzal D-sorbite and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, the preferred silica of nucleating agent, two benzals D-sorbite (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
Rheological agent in the auxiliary agent can ensure that polymer has good brushability and appropriate during film Coating thickness, the sedimentation of solid particle, can improve its redispersibility comprising but be not limited only to following when preventing storage A kind of or several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, lithium chloride, sulfuric acid Sodium, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, aluminium alkoxide, Titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanate derivates, acrylic acid Lotion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferred organobentonite of rheological agent, polyethylene wax, hydrophobic Modified alkaline swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, and one As be 0.1-1wt%.
Dynamic regulation agent in the auxiliary agent, can promote the dynamic of dynamic aggregation object, be usually with freely Hydroxyl either free carboxyl group or can provide or receive the compound of electronics pair, include but are not limited to water, sodium hydroxide, Alcohol (including silanol), carboxylic acid, lewis acid, lewis base etc..This analog assistant can adjust the dynamic of polymer, to obtain The expected performance of optimization.Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt%.
The filler primarily serves following effect in polymer samples：1. reducing the shrinking percentage of molded article, carry Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjusting the viscosity of material；③ Meet different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, improve wearability, improve Heat distortion temperature improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability and chemically-resistant being rotten Corrosion；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The filler, selected from following any or 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, glass microballoon, resin microbeads, foam microspheres, glass powder, cement, Glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramics are fine Dimension, whisker etc..
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：1. natural organic filler, such as skin Hair, natural rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, shellac, chitin, chitosan, Lignin, starch, protein, enzyme, hormone, raw lacquer, timber, wood powder, shell powder, glycogen, xylose, silk etc.；2. synthetic resin is filled out Material, such as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, cellulose acetate, poly- three Fluorine vinyl chloride, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-vinyl acetate c Object, high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine formaldehyde resin, gathers high density polyethylene (HDPE) Amide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, polybutylene terephthalate (PBT), poly- carbon Acid esters, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate, phenolic resin, Tetrafluoroethylene-perfluoro propane copolymer, polyimides, polymethyl acrylate, polymethacrylonitrile, polymethyl methacrylate, Polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, polyvinyl acetate Ester, polyvinyl butyral, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.；3. synthetic rubber filler, such as isoprene rubber, suitable Buna, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorubber, polyacrylate Rubber, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc.；4. synthetic fibers filler, such as viscose fiber, copper ammonia fiber, two Setilose, triethyl fiber, Fypro, polycarbonate, vinal, polyester fiber, polyurethane fiber, Polyacrylonitrile fibre, vinylon, polyvinyl chloride fibre, polyolefine fiber, fluorofibre, fibrillated polytetrafluoroethylene Dimension, aromatic polyamide fibre, aramid fiber or aramid fiber etc..
Wherein, wire feeding does not limit, mainly depending on required material property, preferably calcium carbonate, barium sulfate, cunning Mountain flour, carbon black, graphene, glass microballoon, glass fibre, carbon fiber, natural rubber, chitosan, starch, protein, polyethylene, Polypropylene, polyvinyl chloride, vinyl-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate, Fypro, poly- carbonic acid Ester fiber, vinal, polyester fiber, polyacrylonitrile fibre；Amount of filler used is not particularly limited, generally 1- 30wt%.
In the preparation process of hydridization dynamic aggregation object, spy is not done to the dosage of hydridization dynamic aggregation object each component raw material Other restriction, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.The present invention The manufacturing method of composition be not particularly limited, for example, can be by roller, kneader, extruder, omnipotent blender etc. according to need Additive is blended with hydridization dynamic aggregation object, then carries out the subsequent operation such as foam.
Energy-absorbing method of the present invention based on hydridization dynamic aggregation object, by reasonably selecting in hydridization dynamic aggregation object Type, the content of organic boronic ester bond, inorganic borate key, optional dynamic boracic key and dynamic supermolecule hydrogen bond, energy-absorbing Performance is adjustable on a large scale；By reasonably selecting the topological structure of hydridization dynamic aggregation object molecule, its energy absorption performance also can adjust.Example Such as, when the covalent cross-linking including the included boracic dynamic covalent bond of hydridization dynamic aggregation object molecule is below gel point, can lead to It crosses and carries out energy-absorbing and defense of resistance to impact using dilatancy possessed by hydridization dynamic aggregation object (shear thickening effect)；Optional The degree of cross linking of supermolecule hydrogen bond action also below gel point when, hydridization dynamic aggregation object can show more sensitive more layers Secondary dilatancy, to effectively mitigate the vibrations of vibration body, rises to which mechanical energy be lost more by VISCOUS FLOW To the effect of damping energy-absorbing；When forming dynamic covalent cross-linking network and/or hydrogen bond action forms crosslinking and/or molecule inner ring, A variety of boracic dynamic covalent bonds and hydrogen bond action can be collectively as that can sacrifice key, a large amount of energy of absorption at break under external force It measures and assigns polymer material with excellent energy absorption performance.
Meanwhile hydridization dynamic aggregation object of the present invention for energy-absorbing also has both self-repair function.By suitably organizing sorting Design is selected and is formulated, it can mimic biology bulk damage heals while energy-absorbing principle so that material can be to internal or outer Portion's damage carries out self-healing, eliminates hidden danger, extends the service life of material, in the fields such as military project, medicine, electronics, bionical Show huge application potential.
Energy-absorbing method of the present invention based on hydridization dynamic aggregation object, can be widely applied to damper, padded coaming, Damping material, defense of resistance to impact material, athletic protective article, army and police's protective article, and have both self-repairability and energy-absorbing function Coating, plank, binder, sealing material, toughness material, tough elastomer material, squeegee etc., military aerospace equipment, The fields such as functional coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material, all embody and attract people's attention Application effect.
Hydridization dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
By the polyethylene glycol (average molecular weight is about 2000Da) and 2 molar equivalents of 1 molar equivalent both ends alkenyl sealing end 3- sulfydryls -1,2-PD is dissolved in dimethylformamide (DMF), in 0.1 molar equivalent photochemical catalyst benzoin dimethylether (BDK) In the presence of reacted in the UV lamp in room temperature, obtain the polyethylene glycol blocked with glycol.
Under nitrogen protection, 1 molar equivalent 2- formylphenylboronic acids and anhydrous magnesium sulfate are scattered in absolute methanol, 0 The methanol solution containing 4 molar equivalent ethylenediamines is instilled at DEG C, is stirred 30 minutes, then is warmed to room temperature and is continued stirring 3 hours.It will be anti- It answers solution to be cooled to 0 DEG C again, the sodium borohydride of 3 molar equivalents is added, then be warmed to room temperature and continue to be stirred to react 1 hour.It will be anti- It answers liquid to concentrate, deionized water and sodium bicarbonate solution is added, dichloromethane is used in combination to extract, except obtaining compound 1a after solvent.
By the polyethylene glycol, 3 molar equivalent 1a, 2 molar equivalent tetrahydroxy, two boron with glycol sealing end obtained by 5 molar equivalents It is dissolved in methanol, after room temperature condition stirs evenly, a small amount of NaOH aqueous solutions is added dropwise to and continues stir about after 30-40 minutes, by institute It obtains solution to be poured into suitable mold, and sample molds is placed in 50 DEG C of baking ovens and remove solvent, finally obtained after cooling transparent Membranaceous hydridization dynamic aggregation object sample.Resulting polymers sample tensile strength is 1.8MPa, elongation at break 620%.With Protection pad use is made in the material, for buffering foreign impacts power.Sample is crushed after breaking, later by fragment shape reclaimed materials It is placed in 50 DEG C of mold after pressing 4-6h, can form a film, be reused again.
Embodiment 2
By 2 molar equivalent compound 2- aminomethyl phenyls boric acid and 1 molar equivalent hexamethylene diisocyanate in dichloromethane In fully react, obtain compound 2a.
3 molar equivalent compound 2a and 2 molar equivalent boric acid are dissolved in toluene, and are slowly added into containing 6 molar equivalents The tetrahydrofuran solvent of tetraethylene-glycol, divides water to react under reflux conditions, obtains corresponding hydridization dynamic aggregation object.
The hydridization dynamic aggregation object has the effect of " shear thickening ", can be used for damping shock resistance.
Embodiment 3
Three ether of dichloro and excessive sodium azide are dissolved in tetrahydrofuran, converting chlorine atom to azido is obtained by the reaction Compound 3a.By 4- [(1,3- dihydro -1- hydroxyl -2,1- benzoxaborole heterocycle pentane -5- bases) oxygroup] benzonitriles and fourth two Alcohol is dissolved in toluene, and compound 3b is obtained by the reaction in reflux water-dividing.
By 20 molar equivalent compound 3a, 17 molar equivalent compound 3b, 2 molar equivalent three (2- cyanoethyls) borates, 100 molar equivalent zinc chloride are dissolved in DMF, and ultrasound 5 minutes, are warming up to 125 DEG C of stirrings at room temperature after enabling each component be sufficiently mixed Reaction obtains the hydridization dynamic aggregation object of the present invention.100 mass parts of resulting polymers and 15 mass parts montmorillonites are blended, are obtained To the hydridization dynamic aggregation compositions of the present invention.Obtained polymer composition sample is paste, and case hardness is relatively low, tool There are lower fusing point and good thermal stability, using the material as the interlayer of explosion-proof product, for providing excellent impact resistance Energy.
Embodiment 4
The aqueous hydrochloric acid solution that pH is 2.5 is added in 2 molar equivalents (3- aminopropyls) dimethylethoxysilane, at room temperature Stirring obtains the aqueous solution of the hydroxyl raw material containing silicone hydroxyl after hydrolysis completely.The ethyl of 1 molar equivalent is added to solution Boric acid, dehydrochlorination after the reaction was complete, obtains compound 4a.By 3 molar equivalents (3- aminopropyls) dimethylethoxysilane The aqueous hydrochloric acid solution that pH is 2.5 is added, stirs at room temperature, after hydrolysis completely, the boric acid of 1 molar equivalent is added, the reaction was complete Dehydrochlorination afterwards obtains compound 4b.
By the amino-terminated silicone oil of 50 molar equivalent 4a, 10 molar equivalent 4b, 35 molar equivalents, (average molecular weight is It 1000Da) is blended with 100 molar equivalent hexamethylene diisocyanates, is calculated as 100 mass parts, adds 1 mass of water-soluble Organic silicone oil, 2 mass parts water and 30 mass parts polyvinylpyrrolidone particles, are uniformly mixed and quickly stirring extremely generates bubble, Cure 15 minutes at room temperature, then cure 2 hours at 80 DEG C to get to hydridization dynamic aggregation object foamed product of the invention. Gained foam tensile intensity 2.1MPa is broken rate elongation 1270%, density 95kg/m3, the damping for making electronic product is anti- Sheath, while there is certain moisture absorption moisture resistance.
Embodiment 5
1 molar equivalent boric acid, 4 molar equivalent trimethylolpropane allyl ethers and 0.1 molar equivalent one are hydrated Niter cake mixing be placed in the reaction vessel with water knockout drum and condenser pipe, under microwave condition, respectively at 60 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C are respectively reacted two minutes, are cleaned by distilling, are obtained the intermediate product of alkenyl sealing end.1 mole is worked as again 3- sulfydryl -1,2- the propylene glycol of amount gained intermediate product and 3 molar equivalents is under the catalysis of 0.1 molar equivalent BDK in ultraviolet lamp Lower reaction obtains polyalcohol intermediate product 5a.
1 molar equivalent 5a and 6 molar equivalent 2- amino phenyl boric acids are dissolved in toluene, it is anti-at 70 DEG C that anhydrous magnesium sulfate is added It answers 16 hours, obtains the corresponding amino-terminated polymer containing boracic dynamic covalent bond.Amino-terminated by gained contains There is the polymer of boracic dynamic covalent bond to be reacted again with the ethyl isocyanate with amino equimolar equivalent, obtains containing boric acid ester group With the hydridization dynamic aggregation object of urea groups.Gained hydridization dynamic aggregation object tensile strength be 2.0MPa, elongation at break 638%, There are certain flexibility, case hardness moderate.Using the material as packaging material, it to be used for bumper and absorbing shock.
Embodiment 6
With the silane surface modified silica of three ethoxy of vinyl, then with 3- sulfydryls -1,2-PD in triethylamine catalysis Under the conditions of, addition reaction is clicked by mercaptan-alkene hydrocarbon, glycol modification silica 6a is made.
Polybutadiene, 4- mercaptophenyl boronic acids, 6- sulfydryl hex- 1- alcohol, 2- (t-butoxycarbonyl-amino) ethyl mercaptan, light are drawn Hair agent BDK reacts in tetrahydrofuran, keeps alkenyl and 4- mercaptophenyl boronic acids, 2 mercapto ethanol, 2- (tertiary fourth oxygen in polybutadiene Boc-amino) ethyl mercaptan, BDK molar ratio be about 100:20:10:20:1, obtain modified polybutadiene.
100 mass parts of gained modified polybutadiene are dissolved in toluene, are added 30 mass parts glycol modification silica 6a, 3 The neopelex of mass parts metaboric acid and 0.5 mass parts continues stir about half an hour, later sets mixed liquor It is dried except solvent under the conditions of 50 DEG C in suitable mold, complete postposition must be dried and be cooled to room temperature, be dispersed with The hydridization dynamic aggregation object based on polybutadiene of silica.By 100 mass parts resulting polymers and 4 mass parts graphenes or Carbon nanotube is fully blended, and obtains corresponding hydridization dynamic aggregation compositions.Each base part is made with this elastomeric material, For buffering energy-absorbing, while it can be used as electricity, heat, stress sensing material.
Embodiment 7
10 molar equivalent methyl-boric acids and 2 molar equivalent boric acid are heated to 80 DEG C, be added dropwise to wherein it is a small amount of go from Then sub- water and acetic acid are added dropwise to 10 molar equivalent both ends with hydroxy-end capped silicone oil (average molecular weight in the state of stirring About 900Da) and 3 molar equivalent both ends with hydroxy-end capped polyethylene oxide (average molecular weight is about 1200Da), heating In the state of stir 30 minutes, after so that each component is sufficiently mixed uniformly, triethylamine is added as catalyst, the reaction was continued 2h is obtained To polymer fluid.The apparent viscosity of polymer fluid is tested using rotational viscometer, wherein test temperature 25 DEG C, constant shear rate is 0.1s-1, the apparent viscosity for measuring polymer fluid is 35Pas.The hydridization dynamic aggregation of this structure Logistics body embodies apparent dynamic characteristic and " shear thickening " property, can apply on textile or in foams, system Defense of resistance to impact articles for use are made, such as uses clothes as movement or is used as movement with protection pad.
Embodiment 8
The high molecular weight poly-β-hybroxybutyric acid (average molecular weight about 300000Da) of 1 molar equivalent is dissolved in dichloromethane Alkane instills the mixed solution containing 1000 molar equivalent p-methyl benzenesulfonic acid and 10000 molar equivalent 1,4-butanediol.It is anti-at room temperature After answering 10 hours, with methanol extraction and product is rinsed, obtains the low molecular weight poly-β-hybroxybutyric acid (average mark that both ends are hydroxyl Son amount about 3000Da).
Under the conditions of anhydrous and oxygen-free, first take 10 molar equivalent resulting polymers and 7 molar equivalent dichlorophenyl borines fully mixed Conjunction is placed in mold, add by mold be placed in the mixed atmosphere of boron chloride/nitrogen in 120 DEG C cure 2 hours, obtain base In the hydridization dynamic aggregation object of poly-β-hybroxybutyric acid.Gained hydridization dynamic aggregation object tensile strength 13.4MPa is broken rate elongation 630%.Using the material as packaging material, it to be used for bumper and absorbing shock.In addition, the material is degradable, can be widely used for disposably producing The bumper and absorbing shock of product.
Embodiment 9
11 molar equivalents are dissolved in toluene to benzene hypoboric acid and 10 molar equivalent threitols, are reacted under the conditions of reflux water-dividing After completely, 2 molar equivalent 3,4-Dihydroxybenzoic acid are added, the reaction was continued, obtains oligomer 9a.By 1 molar equivalent chemical combination Object 9a and the reaction of 2 molar equivalent 3- dimethyl methoxy silanes, obtain the oligomer 9b blocked with methoxy silicon substrate.
Under nitrogen protection, by the oligomer 9b blocked with methoxy silicon substrate, the 5 molar equivalent boric acid obtained by 15 molar equivalents It is fully blended, reacts 24 hours at room temperature, obtain containing there are two types of the hydridization dynamic aggregation objects of boracic dynamic covalent bond.Gained Polymer material, tensile strength 15.7MPa, stretch modulus 18.9MPa have certain surface strength and rigidity.With this Product made of kind material, such as bumper, car damping piece, noise reduction gear, sound panel, for subtracting during use Shake, impact resistance, sound insulation, while enough intensity can be provided.
Embodiment 10
The 4- xenyl formyl chlorides of acrylic acid 2- amino-ethyls ester and equimolar equivalent are dissolved in dichloromethane, in triethylamine The acrylate monomer 10a of amide bond is obtained under catalysis.By four hydroxyls of acrylic acid -2,3- dihydroxy propyl ester and equimolar equivalent Two boron of base divides water to react in reflux in toluene, obtains acrylic ester monomer 10b.By 4- hydroxybutyl acrylates respectively with second Ylboronic acid dehydration in toluene obtains the acrylate monomer 10c of the covalent bond of dynamic containing boracic.
100 molar equivalent n-butyl acrylates, 50 molar equivalent monomer 10a, 2 molar equivalent monomer 10b, 3 moles are worked as Amount monomer 10c is sufficiently mixed and records volume of mixture, by 1 molar equivalent of azo-bis-isobutyl cyanide, pore-foaming agent hexamethylene, emulsifier After Span80 is sufficiently mixed, it is slowly dropped into calcium chloride solution.Keep acrylate mixture：Hexamethylene：The volume ratio of Span80 It is 8:3:5, it is 1 to keep the ratio between oil water phase volume:4.After being added dropwise, continue stirring 1 hour, it is rear to stop stirring, by solution It is transferred in mold.After being reacted 10 hours at 85 DEG C, decompression foaming.It demoulds after being dried under vacuum to constant weight, is based on accordingly The hydridization dynamic aggregation object foam of polyacrylate.Gained foamed material tensile strength 1.2MPa is broken rate elongation 1270%, close Degree is 70kg/m3.Using the foamed material as coating or carrier, for buffer protection, sound absorption shock absorbing.
Embodiment 11
The formaldehyde of the phenol of 1 molar equivalent and 1.7 molar equivalents is placed in reaction vessel, sodium hydroxide is added and adjusts body It is pH value between 8-9, regulation system temperature is about 100 DEG C, keeps the temperature 2 hours.Reactant is cooled to 60 DEG C, 0.7 matter is added Part zinc borate, 0.4 the third boric acid of mass parts ring are measured, and the pH value of regulation system is between 5-6.After dissolving half an hour, it is warming up to boiling It rises, is dehydrated after being kept for 1 hour, obtains the polymer based on phenolic resin.
By obtained by 100 mass parts phenolic resin, 0.3 mass parts mass parts Tween-80,5 mass parts are to toluene sulphur Acid injects mold after being sufficiently stirred 30 seconds, and using pentane as foaming agent, foamed solidification obtains corresponding foam in one hour at 80 DEG C Product.With plank made of the material, the use of sound insulation deadener is can be used as, while there is good heat-resisting flame resistance.
Embodiment 12
Under nitrogen protection, amination dimethyl siloxane 12a (average molecular weight about 10000Da, x is added in urea:y About 3:2) it is 8, to keep the molar ratio of urea and amino:10,160 DEG C are to slowly warm up under stirring, after keeping the temperature about 1 hour, drop To room temperature, modified dimethyl polysiloxane 12b is obtained.By the dimethyl silicone polymer 12b of gained and excessive gluconic acid into Row acylation reaction obtains modified dimethyl polysiloxane 12c.It is amino-terminated dimethyl silicone polymer (average mark by both ends 900) son amount is about reacted with 4- (2- carboxy ethyls) phenyl boric acid, obtain the dimethyl silicone polymer 12d blocked with phenyl boric acid base.
By 100 mass parts modified dimethyl polysiloxane 12c, 15 mass parts modified dimethyl polysiloxane 12d, 3 mass Part boric acid is sufficiently mixed, and is dehydrated with being kept the temperature at 120 DEG C, is obtained the hydridization dynamic aggregation object based on dimethyl silicone polymer.
Gained hydridization dynamic aggregation object tensile strength 0.9MPa is broken rate elongation 1160%.Using this elastomer as electricity The sealing element of the component of sub- product has the function of protecting against shock again while waterproof, also acts as graphene, carbon nanotube etc. The base material that stability feature is improved with defense of resistance to impact damping of electricity, heat, strain gauge.
Embodiment 13
Using the methyl isocyanate of equimolar equivalent and N- (2- ethoxys) acrylamide as raw material, under the catalysis of TDBDL Monomer 13a is made in reaction.It, will using 1 molar equivalent trithiocarbonate as chain-transferring agent using 1 molar equivalent AIBN as initiator 50 molar equivalent acrylamides, 15 molar equivalent 3- acrylamidos phenyl boric acids, 35 molar equivalent monomer 13a are in methylene chloride Combined polymerization obtains the random copolymer based on polyacrylamide containing side hydrogen bond group and side boron hydroxyl simultaneously.
By the sodium alginate of the copolymer based on polyacrylamide, 50 mass parts obtained by 100 mass parts, 30 mass parts Polyvinyl alcohol, 5 mass parts boric acid be dissolved in toluene, the hydridization dynamic that the present invention is obtained in dividing water to react under reflux conditions is poly- Close object.Resulting polymers are swollen in water, a kind of hydridization dynamic aggregation object hydrogel can be obtained.Made from the hydrogel Adhesive blocks glue, squeegee, has the function of bumper and absorbing shock.
Embodiment 14
Cyanuric acid and the chloro- 1- hexenes of 6- keep molar ratio 4:1, it is dissolved in anhydrous dimethyl sulphoxide, under potassium carbonate catalysis It is stirred to react at 80 DEG C 15 hours, obtains the olefinic monomer 14a of hydrogen bonds group.10 molar equivalent compound 14a are added Reaction vessel is cooled to 5 DEG C by toluene, and 13 molar equivalent cyclopentadiene are added dropwise in low temperature.It is warming up to back after being added dropwise Stream temperature continues to be stirred to react, and obtains the borneol ene derivative 14b of hydrogen bonds group.Respectively with boric acid triallyl and 4- ethylene Base phenyl boric acid repeats this step instead of compound 14a as raw material, respectively obtains compound 14c, 14d.
15 molar equivalent 14b, 2 molar equivalent 14c, 3 molar equivalent 14d and 30 molar equivalent 1,3- cyclopentadiene are existed It is reacted in dichloromethane under the catalysis of Grubbs bis- generations catalyst, obtains four random copolymer.By above-mentioned copolymer 1 00 Mass parts uniformly mix 220 mass parts of naphthenic oil, 80 mass parts of carbon black, and 2 mass parts of pentaerythrite are sufficiently mixed, and are placed in mold In, 30 minutes are kept the temperature at 160 DEG C, the hydridization dynamic aggregation object based on polynorbornene containing side hydrogen bond group is obtained after cooling Elastomer.
Resulting polymers tensile strength 21MPa is broken rate elongation 1050%.Using the elastomer as packaging material, can use In efficient damping.Meanwhile the product has splendid toughness, and resilience is good, set resistant is small, can carry out large range of drawing It stretches.With good defense of resistance to impact performance, can be used for preparing army and police's protective article.
Embodiment 15
Limonene oxide is extracted from orange peel, it is polymerize with carbon dioxide under the catalytic action of beta-diimine zinc Reaction, obtains makrolon PLimC 15a.1 molar equivalent ethamine, 2.5 molar equivalent dithiothreitol (DTT)s (DTT), 6 moles are worked as (the two volume ratio is 1 to the mixed solution of amount γ-thiobutryolacatone addition ethyl alcohol and 0.5M sodium bicarbonates:1).Reaction is protected in nitrogen It is carried out at 50 DEG C under shield, obtains compound 15b.By the makrolon PLimC 15a and 5 containing 100 molar equivalent side alkenyls Molar equivalent [4- (mercapto methyl) phenyl] boric acid neopentyl glycol ester, 15 molar equivalent 3- sulfydryl -1,2- propylene glycol, 20 moles work as Amount 15b, 60 molar equivalent 3- mercaptopropionic acid N-butyls are dissolved in tetrahydrofuran and are fully blended, in the presence of photoinitiator b DK and It is reacted under the irradiation of ultraviolet lamp, obtains polymer 15c.
100 mass parts resulting polymers 15c and 3 mass parts, three methyl borate are added in small-sized internal mixer and are kneaded After 10min, it is added that 10 mass parts silica, 12 mass parts titanium dioxides, 5 parts by mass of cellulose are nanocrystalline, 0.1 mass parts silicone oil Continuing mixing 20-30min makes additive be sufficiently mixed uniformly with sizing material, takes out sizing material later, is placed in suitable mold, It places in 80 DEG C of vacuum drying ovens and is further reacted for 24 hours, be cooled to be placed at room temperature for 30min later, be removed from the molds sample Product, finally obtaining soft hydridization dynamic aggregation object material can be prepared into not with good plasticity according to die size The product of similar shape, and it can be recycled.
Resulting polymers tensile strength 7.1MPa is broken rate elongation 1380%, using the material as packaging material, for delaying Eat up part of shake.In addition, the material is renewable raw materials, the bumper and absorbing shock of disposable products can be widely used for.
Embodiment 16
4- (bromomethyl) phenyl boric acid is dissolved in tetrahydrofuran, excessive sodium azide is added, compound 16a is obtained by the reaction.
At -78 DEG C, 1 molar equivalent δ-valerolactone is instilled into the tetrahydrofuran containing 1 molar equivalent lithium diisopropylamine Solution after stirring, is added the toluene solution of the 3- propargyl bromides containing 1.1 molar equivalents, is reacted at -40 DEG C. After reaction, by crude product at 140 DEG C short-path distillation, obtain internal ester monomer 16b.Under anhydrous condition, by 50 molar equivalent lactones Monomer 16b and 100 molar equivalent 6-caprolactones are dissolved in toluene, in 1 molar equivalent initiator 2,2- dibutyl -2- tin -1,3- bis- Oxygen cycloheptane reacts under causing in 20 DEG C, obtains the random copolymer based on polyester that the hydroxy-end capped side group in both ends contains alkynyl.
Gained copolymer and compound 16a are dissolved in tetrahydrofuran, it is 1 to keep the molar ratio of side alkynyl and 16a:1, in iodine Change and the copolymer based on polyester containing side boron hydroxyl is obtained by the reaction in 35 DEG C under cuprous and pyridine catalysis.By gained copolymer It is dissolved in tetrahydrofuran with 2,5- dehydration -1- nitrine -1- deoxy-D-glucose alcohol, keeps side alkynyl and 2,5- dehydration -1- nitrine - The molar ratio of 1- deoxy-D-glucose alcohol is 1:1, it is obtained by the reaction containing side hydroxyl in 35 DEG C under the catalysis of cuprous iodide and pyridine The copolymer based on polyester of base.The copolymer containing pendant hydroxyl group of gained is dissolved in dichloromethane, in dibutyl tin cinnamic acid It is reacted with ethyl isocyanate under the catalysis of tin (DBTDL), it is about 3 to keep the molar ratio of pendant hydroxyl group and ethyl isocyanate:1 obtains together The polymer of Shi Hanyou side carbamateyls and pendant hydroxyl group.
By the copolymer based on polyester containing side carbamateyl and pendant hydroxyl group obtained by 100 mass parts, 70 mass The copolymer based on polyester containing side boron hydroxyl and 5 mass parts diboranes of part gained fully react.Resulting polymers are molten It is swollen to be placed in mold and freezed completely at -80 DEG C in Isosorbide-5-Nitrae-dioxane solvent, aspiration pump is opened at -50 DEG C, remains dry Dry air pressure is less than 50 μ atm 24 hours, and obtained foamed material is placed in drying in 20 DEG C of vacuum drying chambers, is extracted all molten Agent obtains corresponding foamed material.The hydridization dynamic aggregation object foam tensile intensity 14.3MPa of gained is broken rate elongation 1020%, density 93kg/m3.The foamed material can be used as coating or carrier, for buffer protection, sound absorption shock absorbing.
Embodiment 17
100 mass parts polyvinyl chloride are dissolved in tetrahydrofuran, the sodium azide of 10 mass parts is added, is obtained by the reaction containing portion Divide the polyvinyl chloride of side azido.By the polyvinyl chloride of gained and 2- propargyl-N- butyl carbamates and 3- butine -1- Alcohol is dissolved in tetrahydrofuran, keeps azido and 2- propargyl-N- butyl carbamates in polyvinyl chloride, 3- butyne-1-ols Molar ratio is 10:7:3, under the catalysis of cuprous iodide and pyridine, be obtained by the reaction at 35 DEG C containing side carbamateyl and The modified polyvinyl chloride of pendant hydroxyl group.
By 100 mass parts of polyvinyl chloride of gained, 70 mass parts of epoxidized soybean oil, 50 mass parts of tricresyl phosphate, boron Sour 1 mass parts, 2 mass parts of phenylboric acid are uniformly mixed, and are placed in mold and are kept the temperature 30 minutes in 180 DEG C, are based on after cooling The hydridization dynamic aggregation object elastomer of polyvinyl chloride.Obtained hydridization dynamic aggregation object sample tensile strength is 12MPa, and fracture is stretched Long rate is 679%, and protection pad, which is made, with the material uses, for buffering foreign impacts power.After its appearance is damaged, at 100 DEG C Under the conditions of can be molded again, recycled and reused.
Embodiment 18
By cladodification polyethyleneimine (average molecular weight about 7000Da) and glycolic, acetic acidreaction, polyethyleneimine is kept The molar ratio of middle Amino End Group and glycolic, acetic acid is 10:2:7, obtain the cladodification polyethyleneimine that end group is hydroxyl and amino.Nothing Under water condition, the polyethyleneimine of gained and 4- formyl chlorophenylboronic acids are dissolved in dichloromethane, keep the end in polyethyleneimine The molar ratio of amino and 4- formyl chlorophenylboronic acids is 1:1, it is hydroxyl and boron hydroxyl that end group is obtained by the reaction under the catalysis of pyridine Polyethyleneimine.The boric acid of 100 mass parts resulting polymers and 1 mass parts is uniformly mixed, thermal dehydration solidification is obtained to contain The covalently cross-linked hydridization dynamic aggregation object of boron dynamic.With the adhesive of the polymer, glue, squeegee are blocked, is had slow Eat up part of the effect of shake.
Embodiment 19
1 molar equivalent boric acid and 3 molar equivalent allyl hydroxyethyl ethers are dissolved in toluene, held in the reaction with water knockout drum Back flow reaction in device obtains triolefin hydrocarbon compound 19a.4- vinylphenylboronic acids and 3- allyloxy -1,2- propylene glycol are dissolved in Toluene, the back flow reaction in the reaction vessel with water knockout drum obtain double olefin compound 19b.It, will under the conditions of anhydrous and oxygen-free Isosorbide-5-Nitrae-pentadiene -3- thiol reactions of ethyl isocyanate and equimolar equivalent obtain side group and carry thiocarbamate base Double olefin compound 19c.
By 2 molar equivalent 19a, 5 molar equivalent 19b, 5 molar equivalent 19c and 13 2,2 '-(1,2- second diyls of molar equivalent Dioxygen generation) double ethyl mercaptans mix in DMF, and using benzoin dimethylether as photoinitiator, illumination in the UV lamp is fully reacted, and is obtained To the hydridization dynamic aggregation object of the present invention.Resulting polymers tensile strength 1.9MPa, elongation at break 1050% are made with the material For packaging material, device outer case, has the function of damping, buffering.
Embodiment 20
5- chloromethyl -2- oxazolidones and excessive sodium azide are dissolved in tetrahydrofuran reaction, obtain turning chlorine atom Turn to the hydrogen bond group 20a of azido.By 1 molar equivalent polyacrylonitrile (average molecular weight about 10000Da), 20 molar equivalents Object 20a is closed, 5 molar equivalents 2,5- dehydration -1- nitrine -1- deoxy-D-glucoses alcohol, 100 molar equivalent zinc chloride are dissolved in diformazan Base formamide, at room temperature ultrasound be warming up to 125 DEG C after enabling each component be sufficiently mixed within 5 minutes and be stirred to react, obtain containing side hydrogen bond The modified polyacrylonitrile of group and pendant hydroxyl group.
By obtained by 100 mass parts modified polyacrylonitrile and 5 mass parts phenyl -1,4- hypoboric acid, 1 mass parts boric acid it is abundant It is blended, is dissolved in dimethylbenzene, thermal dehydration is obtained by the reaction with the covalently cross-linked polymer of boracic dynamic.By gained cross-linked polymer It the 1- ethyl-3-methylimidazoles tetrafluoroborate and solvent dimethylformamide of quality such as swells in, then removes solvent, gathered Acrylonitrile/1- ethyl-3-methylimidazole tetrafluoroborate ionic gels.
The modulus of ionic liquid gel prepared by the embodiment is in 43kPa, and strain can reach 9 times, and fracture strength exists 104kPa.Using this ionic liquid gel as protective pad, it to be used for the impact of anti-external forces.
Embodiment 21
By 1 molar equivalent phenyl -1,3, tri- boric acid of 5- and 3 molar equivalent 3- chlorine-1,2-propylene glycols are dissolved in toluene, are flowing back At a temperature of divide water to react, obtain compound 21a.1 molar equivalent metaboric acid is reacted with 3 molar equivalent ethylene chlorhydrins and is dissolved in first Benzene divides water to react at a reflux temperature, obtains compound 21b.The third ammonia of alkynes and 5- hexynic acids are subjected to acylation reaction, obtain chemical combination Object 21c.21a, 21b are dissolved in tetrahydrofuran and excessive reaction of sodium azide respectively, obtain blocking with azido accordingly Compound 21d, 21e.
Bifunctional initiator 1 is generated with 2- bromine isobutyl acylbromides and glycol reaction, bis- (the bromine isobutyl acyl-oxygen) ethane of 2- draw The ATRP reactions for sending out n-butyl acrylate, obtain the polyacrylic acid N-butyl that both ends are blocked with bromine atom.By the both ends of gained with The polyacrylic acid N-butyl of bromine atom sealing end is dissolved in tetrahydrofuran, with excessive reaction of sodium azide, obtains both ends with azido The polymer of sealing end.The polyacrylic acid N-butyl that both ends obtained by 15 molar equivalents are blocked with azido and 30 molar equivalents 21c is dissolved in tetrahydrofuran, under the catalysis of cuprous iodide and pyridine, is reacted at 35 DEG C.After complete reaction, 5 moles are added The reaction was continued by equivalent 21d and 5 molar equivalent 21e, obtains the hydridization dynamic aggregation object of the present invention.Protection pad, which is made, with the material makes With for buffering foreign impacts power.
Embodiment 22
By maleic anhydride grafted polyethylene, 4- aminomethyl phenyls ylboronic acid, 1,3- dihydro -1- hydroxyl -2,1- Ben Bing Evil boron -6- Amine, 3- amino -1H- pyrazolos [3,4-b] pyridines keep maleic anhydride side group in polyethylene, 4- ammonia in 170 DEG C of melt blendings Methylphenylboronic acid, 1,3- dihydro -1- hydroxyl -2,1- Ben Bing Evil boron -6- amine, 3- amino -1H- pyrazolos [3,4-b] pyridine Molar ratio is 10:2:1:7, obtain the polyethylene containing side boron hydroxyl and side hydrogen bond group.By in embodiment 19 gained carry The polycyclic octene of pendant hydroxyl group carries out hydrogenation reaction, obtains the polyethylene with pendant hydroxyl group.
By the poly- second containing side boron hydroxyl and side hydrogen bond group obtained by 100 mass parts low density polyethylene (LDPE)s, 20 mass parts The polyethylene with pendant hydroxyl group, 2 mass parts boric anhydrides obtained by alkene, 20 mass parts are placed in 120 DEG C of melting dehydrations in mold, temperature Degree is down to 70-100 DEG C, and then mold is placed in autoclave, is passed through supersaturated carbon dioxide.Pressurized, heated to 160 DEG C, Decompression makes its expanded foamed molding after 12 minutes, and the hydridization dynamic aggregation object foamed product based on polyethylene is obtained after demoulding.
Resulting polymers foam tensile intensity 4.2MPa is broken rate elongation 830%, density 95kg/m3.Using the material as Packaging material, device outer case, have the function of damping, buffering.
Embodiment 23
By polyvinylpyrrolidone (average molecular weight about 14000Da) and etc. the potassium hydroxide of quality be dissolved in deionized water In, it is reacted 24 hours in 150 DEG C.It waits after the completion of reacting, removes device, after reaction solution is cooled to room temperature, by being total to after reaction Mixed liquid filtering, clear filtrate is uniformly mixed with DMF, DMF and water under the conditions of 60 DEG C in vacuum distillation removing mixed solution, In the dichloromethane that the solid residue that vacuum distillation obtains is dissolved in again, filter mixed liquor removes unreacted potassium hydroxide, Air-distillation removes the solvent in filtrate again.The solid residue that distillation obtains is dissolved in deionized water, with 0.1M HCl tune Save pH to 2-3, after carboxylic acid reaction one hour, then with interception be 3500Da bag filter different pH acid solution (pH=3, PH=4, pH=5) and water in gradient dialyse, freeze-drying, obtain the polyvinylpyrrolidone 23a of solid powder part open loop.Through nuclear-magnetism Characteristic peak integrates in hydrogen spectrum, and it is about 10% to calculate open loop rate.By the polyvinylpyrrolidone 23a of the part open loop of gained with and 4- (2- hydroxyethyls) phenyl boric acid of side carboxyl equimolar equivalent reacts under the catalysis of DCC and DMAP, obtains modified poly ethylene Pyrrolidones 23b.
By 1 molar equivalent modified polyvinyl pyrrolidone 23b, 5 molar equivalent diglycerol ethers, 3 molar equivalent sucrose, The quality sum of 10 molar equivalent mebors is denoted as 100 mass parts, is dissolved in deionized water/methanol mixed solvent, adds Enter 0.5 mass parts Silane coupling agent KH550,0.3 mass parts neopelex, 10 mass parts glass micro-fibers, at 50 DEG C Under the conditions of stirring 10min after, be added 0.1 mass parts hydroxyethyl cellulose, continue stirring 10-20 minutes, then can be disperseed There are the polymer samples of glass micro-fibers to be placed in sample and carry out within 24 hours in 50 DEG C of baking ovens removing solvent, obtains having after cooling certain Viscoplasticity, the higher agar shaped polymer sample of case hardness.Resulting polymers tensile strength is 3.7MPa, elongation at break It is 543%.Using the material as coating or squeegee, for buffer protection, energy-absorbing shock absorbing.
Embodiment 24
Under the conditions of anhydrous and oxygen-free, 1 molar equivalent compound 24a is dissolved in dichloroethanes, is added and contains 1.2 molar equivalents three The hexane solution of boron chloride, reaction vessel is closed, it is reacted 12 hours in 110 DEG C.After reaction, it is removed under reduced pressure volatilizable Property substance, again with toluene extraction and is recrystallized to give compound 24b in n-hexane.By the compound obtained by 1 molar equivalent 24b is dissolved in dichloromethane, and the trimethylmethoxysilane that 10 molar equivalents are added reacts 48 hours with 45 DEG C.After reaction, Volatile material is removed under reduced pressure, and in dichloromethane/n-hexane (70:30) in the mixed solvent recrystallizes, and obtains chlorine atom It is converted into the compound 24c of methoxyl group.
By the change obtained by the hydroxy-end capped polyethylene glycol of 2 molar equivalents (average molecular weight is about 500Da), 1 molar equivalent It closes object 24c and is dissolved in toluene, be placed in the reaction vessel with water knockout drum, except methanol reacts under reflux temperature, obtain containing two cyclopentadienyls The polyethylene glycol dihydric alcohol of iron boric acid ester group.The hydroxy-end capped polyethylene glycol of 1 molar equivalent boric acid and 3 molar equivalents is (average Molecular weight is about 500Da) it is dissolved in toluene, it is placed in the reaction vessel with water knockout drum, small molecular alcohol reaction is taken off under reflux temperature, Obtain the polyethylene glycol trihydroxylic alcohol containing boric acid ester group.
By the polyethylene glycol dihydric alcohol obtained by 27 molar equivalents, the polyethylene glycol trihydroxylic alcohol obtained by 2 molar equivalents, 30 moles Equivalent 1,5- naphthalene diisocyanates are blended, and under the catalysis of DBTDL, in 80 DEG C of reactions, obtain the hydridization dynamic based on polyurethane Polymer.Using the material as coating, for buffer protection, sound absorption, while having the function of uvioresistant radiation protection.
Embodiment 25
2- (N, the N- dimethylaminomethyl) phenyl boric acids of 1 molar equivalent and 2 molar equivalent 2- methylaminoethanols are dissolved in first Compound 25a is obtained by the reaction in benzene, reflux water-dividing.By two boron of tetrahydroxy of 1 molar equivalent and 2 molar equivalent 3- methylaminos -1,2- Propylene glycol is dissolved in toluene, and compound 25b is obtained by the reaction in reflux water-dividing.3 molar equivalent bisphenol A diglycidyl ethers, 2 moles are worked as Amount polyethylene glycol oligomer (molecular weight is about 1000Da) and catalyst boron trifluoride ether are sufficiently mixed, and the dosage of catalyst is The 1% of polyethylene glycol quality.Mixture is reacted at 80 DEG C, obtains both ends with the epoxy polymer of epoxy radicals end-blocking.
By the compound of the compound 25a and 1 molar equivalent of epoxy polymer and 1 molar equivalent obtained by 2 molar equivalents 25b, which is sufficiently mixed, to be placed in mold, is to slowly warm up to 160 DEG C and is kept the temperature 2 hours, then is cooled to 120 DEG C, heat preservation solidification 2 hours And compression molding, obtain corresponding hydridization dynamic aggregation Tetramune.Resulting polymers tensile strength of material 4.3MPa, fracture extend Rate 1880%.The material can be used for defense of resistance to impact, such as the protective film protective case for dropping from the air and dropping article.
Embodiment 26
99%) and ethyl isocyanate and 2- benzene second by polyvinyl alcohol, (average molecular weight about 150000Da, alcoholysis degree is higher than Based isocyanate reacts in anhydrous dimethyl sulphoxide, and it is 4 to keep the molar ratio of polyvinyl alcohol pendant hydroxyl group and isocyanate group:1, It is 9 to keep the molar ratio of ethyl isocyanate and 2- phenethyl isocyanates:1, it obtains containing carbamate groups but tool in side group There are two types of the polyvinyl alcohol of different end group.
By polyvinyl alcohol, the 2 mass parts Boratex (Na obtained by 100 mass parts2B2O7), 3 mass parts 4,4'- xenyls two Boric acid, 0.2 mass parts zinc oxide, 0.1 mass parts stearic acid, 0.1 mass parts irgasfos 168,0.2 mass parts antioxidant 1010, 0.2 mass parts di-n-butyltin dilaurate after mixing, is added in small-sized extruder and carries out extrusion blending, extrusion temperature It is 80-100 DEG C, after obtained extrusion batten is granulated, obtains elastic little particle, can further utilize moulding press sample preparation. Obtained hydridization dynamic aggregation object sample tensile strength is 8.4MPa, elongation at break 890%.Using the material as lining Pad is used for damping protecting against shock.
Embodiment 27
Two dimethyl carbonates of 6- amino -1- hexanols and equimolar equivalent are dissolved in tetrahydrofuran, compound is obtained by the reaction 27a.Compound 27a and excessive boric acid are dissolved in toluene, divides water to react under counterflow condition, obtains compound 27b.
4- (3- cyclopropyl urea) phenylboric acid pinacol ester is hydrolyzed in 20% acetic acid solution, obtains 4- (3- rings third Base urea) phenylboric acid.Again by 100 mass parts vinyl alcohol-vinyl acetate random copolymers (average molecular weight about 100000Da, Alcoholysis degree is about 40%) and 4- (3- cyclopropyl urea) phenylboric acid obtained by 5 mass part compound 27b, 5 mass parts is in toluene It is fully blended, divides water to react under counterflow condition, obtain the hydridization dynamic aggregation object of the present invention.
Obtained hydridization dynamic aggregation object tensile strength 2.3MPa, elongation at break 780%.Using the material as airborne With air-drop product packaging, for buffering protecting against shock.
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 (16)

1. a kind of energy-absorbing method based on hydridization dynamic aggregation object, which is characterized in that a kind of hydridization dynamic aggregation object is provided, and with It carries out energy-absorbing as energy-absorbing material, and the hydridization dynamic aggregation object contains at least one organic boronic ester bond and at least simultaneously A kind of inorganic borate key；Wherein the organic boronic ester bond contains at least one comprising structure shown in formula (1), described Inorganic borate key contains at least one comprising structure shown in formula (2)：
Wherein, X is selected from carbon atom or silicon atom；K1、K2It is each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine Atom, oxygen atom, sulphur atom, boron atom, nitrogen-atoms, silicon atom, and K1、K2In it is at least one selected from sulphur atom, boron atom, nitrogen Atom, silicon atom；A is and K1、K2ConnectedNumber, work as K1、K2For hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine Atomic time, a 0, there is no the connections other than being connect with boron atom；Work as K1、K2For oxygen atom, sulphur atom when, a 1；Work as K1、K2 For boron atom, nitrogen-atoms when, a 2；Work as K1、K2For silicon atom when, a 3；
Wherein,It is expressed as at least one of group and connection；The organic boronic ester bond and inorganic borate key are miscellaneous Change dynamic aggregation object molecule aggregation or polymerization and crosslinked tie point.
2. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 1, which is characterized in that described is miscellaneous Change the organic boronic ester bond contained by dynamic aggregation object and is selected from organic boronic monoester bond, organic boronic cyclic ester key, organic boronic silicon At least one of ester bond, contained inorganic borate key are selected from organic boronic monoester bond, organic boronic cyclic ester key, organic boron At least one of sour estersil key；
Wherein, the organic boronic monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；L is except direct key (including singly-bound, double bond, three keys), methylene or to be substituted Methylene other than at least divalent linker；
Wherein, the organic boronic cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular organic boronic ester units, the boron atom in the structure with two oxygen atoms simultaneously It need to be connected by boron carbon key with a carbon atom, and at least one organic group is keyed to boron atom by the boron carbon On；
Wherein, the organic boronic estersil key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；
The wherein Inorganic Boron acid monoester key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is connected with a carbon atom by boron carbon key；L is except direct key is (including singly-bound, double Key, three keys), the linker of at least divalent other than methylene or substituted methylene；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
The wherein inorganic boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular inorganic borate unit, the boron atom in the structure with two oxygen atoms simultaneously It is not connected directly with any carbon atom；
Wherein, Z atoms are selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be sulphur atom when, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is When silicon atom, b 3；
Linker L0It is each independently the position being connected with oxygen atom such as any one of lower structure, wherein * expressions：
The wherein inorganic boric acid estersil key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3.
3. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 2, which is characterized in that described is miscellaneous The combination for changing the borate dynamic covalent bond contained by dynamic aggregation object includes at least one of following combination：Organic boronic monoesters The combination of key and Inorganic Boron acid monoester key, the combination of organic boronic monoester bond and inorganic boric acid cyclic ester key, organic boronic monoester bond With the combination of inorganic boric acid estersil key, the combination of organic boronic cyclic ester key and Inorganic Boron acid monoester key, organic boronic cyclic ester key and The combination of inorganic boric acid cyclic ester key, the combination of organic boronic cyclic ester key and inorganic boric acid estersil key, organic boronic estersil key and nothing The combination of machine boric acid monoester bond, the combination of organic boronic estersil key and inorganic boric acid cyclic ester key.
4. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 3, which is characterized in that described is miscellaneous The combination for changing the borate dynamic covalent bond contained by dynamic aggregation object includes at least one of following combination：Aminomethyl phenyl boric acid The combination of cyclic ester key and Inorganic Boron acid monoester key, the combination of aminomethyl phenyl boric acid monoester bond and inorganic boric acid cyclic ester key, aminomethyl The combination of phenyl boric acid monoester bond and Inorganic Boron acid monoester key, the combination of aminomethyl phenyl boric acid cyclic ester key and inorganic boric acid cyclic ester key, The combination of organic boronic estersil key and Inorganic Boron acid monoester key, the combination of organic boronic monoester bond and inorganic boric acid estersil key, has The combination of machine boric acid estersil key and inorganic boric acid cyclic ester key, the combination of organic boronic cyclic ester key and inorganic boric acid estersil key；
Wherein, the aminomethyl phenyl boric acid monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；L is except direct key (including singly-bound, double bond, three keys), methylene or to be substituted Methylene other than at least divalent linker；
The wherein aminomethyl phenyl boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom.
5. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 1, which is characterized in that described is miscellaneous Change and also contains at least one of boric anhydride dynamic covalent bond, dynamic supermolecule hydrogen bond in dynamic aggregation object；Wherein, the boric anhydride Dynamic key is selected from organic boron acid anhydride key, Inorganic Boron acid anhydride key and organic and inorganic boric anhydride key；
Wherein, the organic boron acid anhydride key, for such as lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；
Wherein, the Inorganic Boron acid anhydride key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
Wherein, the organic and inorganic boric anhydride key, selected from such as at least one of lower structure：
Wherein, one of boron atom is connected directly at least one carbon atom by boron carbon key in the structure, and at least one A organic group, which is connected with boron atom by the boron carbon key of formation and accesses polymer chain, forms the dynamic aggregation object molecule；Institute Another boron atom in structure is stated not to be connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
Wherein, the dynamic supermolecule hydrogen bond by simultaneously containing the hydrogen bond group of hydrogen bond donor and hydrogen bond receptor interact and At.
6. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 1, which is characterized in that described is miscellaneous Change and contain supermolecule hydrogen bond in dynamic aggregation object, and the hydrogen bond group for forming supermolecule hydrogen bond contains in following constituent extremely Few one kind：
7. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to claim 1, which is characterized in that described is miscellaneous The glass transition temperature for changing dynamic aggregation object each component is not higher than 25 DEG C.
8. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to any one of claim 1-7, feature exist In wherein the hydridization dynamic aggregation object has following any character：Solution, lotion, cream, gel, ordinary solid, elasticity Body, foamed material.
9. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to any one of claim 1-7, feature exist In, the recipe ingredient for constituting the wherein described hydridization dynamic aggregation object further include it is following any or appoint it is several can additive or can Use object：Other polymers, auxiliary agent, filler；Wherein, the other polymers are selected from following any or appoint several：Naturally High-molecular compound, synthetic resin, synthetic rubber, synthetic fibers；Wherein, the auxiliary agent is selected from following any or appoints several Kind：Catalyst, initiator；Stabilizing additive, including it is antioxidant, light stabilizer, heat stabilizer, dispersant, emulsifier, fire-retardant Agent, chain extender, toughener, coupling agent, crosslinking agent, curing agent, solvent, lubricant, releasing agent, plasticizer, thickener, thixotroping Agent, levelling agent, colorant, fluorescent whitening agent, delustering agent, antistatic agent, biocide mildewcide, foaming agent, nucleating agent, rheological agent, Dynamic regulation agent；The filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.
10. a kind of energy-absorbing method based on hydridization dynamic aggregation object according to any one of claim 1-7, feature exist It is applied to movement and the body protection of daily life and work, army and police's body protection, explosion-proof, airborne in, the energy-absorbing method With air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact, sound insulation, damping.
11. a kind of hydridization dynamic aggregation object, which is characterized in that it is dynamic that the hydridization dynamic aggregation object contains following borate simultaneously At least one of covalent key combination of state：The combination of organic boronic monoester bond and Inorganic Boron acid monoester key, organic boronic monoester bond With the combination of inorganic boric acid cyclic ester key, the combination of organic boronic monoester bond and inorganic boric acid estersil key, organic boronic cyclic ester key and The combination of Inorganic Boron acid monoester key, the combination of organic boronic cyclic ester key and inorganic boric acid cyclic ester key, organic boronic cyclic ester key and nothing The combination of machine boric acid estersil key, the combination of organic boronic estersil key and Inorganic Boron acid monoester key, organic boronic estersil key and inorganic The combination of boric acid cyclic ester key；Including borate dynamic covalent bond be hydridization dynamic aggregation object molecule aggregation or polymerization and crosslinking Tie point；
Wherein, the organic boronic monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；L is except direct key (including singly-bound, double bond, three keys), methylene or to be substituted Methylene other than at least divalent linker；
Wherein, the organic boronic cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular organic boronic ester units, the boron atom in the structure with two oxygen atoms simultaneously It need to be connected by boron carbon key with a carbon atom, and at least one organic group is keyed to boron atom by the boron carbon On；
Wherein, the organic boronic estersil key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；
The wherein Inorganic Boron acid monoester key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is connected with a carbon atom by boron carbon key；L is except direct key is (including singly-bound, double Key, three keys), the linker of at least divalent other than methylene or substituted methylene；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
The wherein inorganic boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, a boron atom forms cyclic annular inorganic borate unit, the boron atom in the structure with two oxygen atoms simultaneously It is not connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3；
Linker L0It is each independently the position being connected with oxygen atom such as any one of lower structure, wherein * expressions：
The wherein inorganic boric acid estersil key, selected from such as at least one of lower structure：
Wherein, the boron atom in the structure is not connected directly with any carbon atom；
When containing the more than one Z atomic time in same formula, each Z atoms are respectively independent；Each Z atoms are each independently selected from Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, sulphur atom, nitrogen-atoms, boron atom, silicon atom, and in same formula extremely A few Z atom is selected from sulphur atom, boron atom, nitrogen-atoms, silicon atom；
B is to be connected with ZNumber, when Z be hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, b 0；When Z is When sulphur atom, b 1；When Z is nitrogen-atoms, boron atom, b 2；When Z is silicon atom, b 3.
12. a kind of hydridization dynamic aggregation object according to claim 11, which is characterized in that the wherein organic boronic list Ester bond is aminomethyl phenyl boric acid monoester bond, wherein the organic boronic cyclic ester key is aminomethyl phenyl boric acid cyclic ester key；
Wherein, the aminomethyl phenyl boric acid monoester bond, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom；L is except direct key (including singly-bound, double bond, three keys), methylene or to be substituted Methylene other than at least divalent linker；
The wherein aminomethyl phenyl boric acid cyclic ester key, selected from such as at least one of lower structure：
Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one organic group Group is keyed to by the boron carbon in boron atom.
13. according to the hydridization dynamic aggregation object described in claim 11, which is characterized in that the hydridization dynamic aggregation object is also Contain at least one boric anhydride dynamic covalent bond；Wherein, the boric anhydride dynamic covalent bond is selected from organic boron acid anhydride key, inorganic boric anhydride Key, organic and inorganic boric anhydride key.
14. a kind of hydridization dynamic aggregation object, which is characterized in that the hydridization dynamic aggregation object contains at least one organic simultaneously Boric acid ester bond and at least one inorganic borate key, and contain supermolecule hydrogen bond simultaneously；Organic boronic ester bond included in it It is hydridization dynamic aggregation object molecule aggregation or polymerization and crosslinked tie point with inorganic borate key；
Wherein the organic boronic ester bond contains at least one comprising structure, the inorganic borate key shown in formula (1) Include structure shown in formula (2) containing at least one：
Wherein, X is selected from carbon atom or silicon atom；K1、K2It is each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine Atom, oxygen atom, sulphur atom, boron atom, nitrogen-atoms, silicon atom, and K1、K2In it is at least one selected from sulphur atom, boron atom, nitrogen Atom, silicon atom；A is and K1、K2ConnectedNumber, work as K1、K2For hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine Atomic time, a 0, there is no the connections other than being connect with boron atom；Work as K1、K2For oxygen atom, sulphur atom when, a 1；Work as K1、K2 For boron atom, nitrogen-atoms when, a 2；Work as K1、K2For silicon atom when, a 3；
Wherein,It is expressed as at least one of group and connection；
Wherein, the dynamic supermolecule hydrogen bond by simultaneously containing the hydrogen bond group of hydrogen bond donor and hydrogen bond receptor interact and At.
15. hydridization dynamic aggregation object according to claim 14, which is characterized in that contain in the hydridization dynamic aggregation object Some supermolecule hydrogen bonds are interacted by least one hydrogen bond group containing following constituent：
16. hydridization dynamic aggregation object according to claim 14, which is characterized in that in the hydridization dynamic aggregation object also Contain at least one of boric anhydride dynamic covalent bond；Wherein, the boric anhydride dynamic covalent bond is selected from organic boron acid anhydride key, Inorganic Boron Acid anhydride key and organic and inorganic boric anhydride key.
CN201710055918.XA 2017-01-25 2017-01-25 A kind of energy-absorbing method based on hydridization dynamic aggregation object Withdrawn CN108341958A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710055918.XA CN108341958A (en) 2017-01-25 2017-01-25 A kind of energy-absorbing method based on hydridization dynamic aggregation object

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710055918.XA CN108341958A (en) 2017-01-25 2017-01-25 A kind of energy-absorbing method based on hydridization dynamic aggregation object

Publications (1)

Publication Number Publication Date
CN108341958A true CN108341958A (en) 2018-07-31

Family

ID=62962153

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710055918.XA Withdrawn CN108341958A (en) 2017-01-25 2017-01-25 A kind of energy-absorbing method based on hydridization dynamic aggregation object

Country Status (1)

Country Link
CN (1) CN108341958A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206550A (en) * 2017-06-30 2019-01-15 翁秋梅 A kind of hydridization supermolecular mechanism dynamic aggregation object
CN109988265A (en) * 2019-04-03 2019-07-09 中国科学院深圳先进技术研究院 The preparation method of selfreparing hydrogel
US10597410B2 (en) * 2018-02-02 2020-03-24 Dipharma Francis S.R.L. Intermediates and process for the preparation of a crystalline form of a topical anti-inflammatory agent
CN113121874A (en) * 2020-01-15 2021-07-16 波音公司 Compositions for use with polysulfide sealants and related methods
WO2021158595A1 (en) * 2020-02-05 2021-08-12 Agrofresh Inc. Antimicrobial compounds and compositions
CN113600160A (en) * 2021-08-05 2021-11-05 厦门大学 TiO with photocatalytic function2Preparation of nanowire/graphene aerogel
CN114560883A (en) * 2022-03-07 2022-05-31 西安石油大学 Boron-containing spiro crude oil treating agent and preparation method thereof
CN114989506A (en) * 2022-05-17 2022-09-02 久耀电子科技（江苏）有限公司 Preparation method of flame-retardant low-dielectric COF/hydrocarbon resin composite material
WO2023014508A1 (en) * 2021-08-05 2023-02-09 ExxonMobil Technology and Engineering Company Reversible epoxy polymer with dynamic boronic bond
CN116426203A (en) * 2023-04-11 2023-07-14 滨州学院 Building surface coating material and preparation method and application thereof
CN116813985A (en) * 2023-07-14 2023-09-29 唐山学院 Early warning material for hydrogen sulfide gas and preparation method thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206550A (en) * 2017-06-30 2019-01-15 翁秋梅 A kind of hydridization supermolecular mechanism dynamic aggregation object
US10597410B2 (en) * 2018-02-02 2020-03-24 Dipharma Francis S.R.L. Intermediates and process for the preparation of a crystalline form of a topical anti-inflammatory agent
CN109988265A (en) * 2019-04-03 2019-07-09 中国科学院深圳先进技术研究院 The preparation method of selfreparing hydrogel
CN109988265B (en) * 2019-04-03 2021-03-02 中国科学院深圳先进技术研究院 Preparation method of self-repairing hydrogel
CN113121874A (en) * 2020-01-15 2021-07-16 波音公司 Compositions for use with polysulfide sealants and related methods
EP3851497A1 (en) * 2020-01-15 2021-07-21 The Boeing Company Compositions for use with polysulfide sealants and related methods
CN113121874B (en) * 2020-01-15 2023-10-24 波音公司 Compositions for use with polysulfide sealants and related methods
US11479655B2 (en) 2020-01-15 2022-10-25 The Boeing Company Compositions for use with polysulfide sealants and related methods
WO2021158595A1 (en) * 2020-02-05 2021-08-12 Agrofresh Inc. Antimicrobial compounds and compositions
WO2023014508A1 (en) * 2021-08-05 2023-02-09 ExxonMobil Technology and Engineering Company Reversible epoxy polymer with dynamic boronic bond
CN113600160A (en) * 2021-08-05 2021-11-05 厦门大学 TiO with photocatalytic function2Preparation of nanowire/graphene aerogel
CN114560883A (en) * 2022-03-07 2022-05-31 西安石油大学 Boron-containing spiro crude oil treating agent and preparation method thereof
CN114560883B (en) * 2022-03-07 2024-01-26 西安石油大学 Boron-containing spiro-type crude oil treating agent and preparation method thereof
CN114989506B (en) * 2022-05-17 2023-08-08 久耀电子科技（江苏）有限公司 Preparation method of flame-retardant low-dielectric COF/hydrocarbon resin composite material
CN114989506A (en) * 2022-05-17 2022-09-02 久耀电子科技（江苏）有限公司 Preparation method of flame-retardant low-dielectric COF/hydrocarbon resin composite material
CN116426203A (en) * 2023-04-11 2023-07-14 滨州学院 Building surface coating material and preparation method and application thereof
CN116813985A (en) * 2023-07-14 2023-09-29 唐山学院 Early warning material for hydrogen sulfide gas and preparation method thereof
CN116813985B (en) * 2023-07-14 2024-02-09 唐山学院 Early warning material for hydrogen sulfide gas and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108341958A (en) A kind of energy-absorbing method based on hydridization dynamic aggregation object
CN107446135B (en) Dynamic polymer with dynamic cross-linked structure
CN107805308B (en) Dynamic polymer with hybrid cross-linked network and application thereof
CN108610486A (en) A kind of energy-absorbing method based on the hybrid cross-linked dynamic aggregation object of combination
CN107805311A (en) A kind of dynamic aggregation thing and its application with hybrid cross-linked network
CN107805309A (en) A kind of dynamic aggregation thing of non-covalent structure and its application
CN108341951B (en) Dynamic polymer with hybrid cross-linked structure and application thereof
CN108341960B (en) Dynamic polymer containing combined dynamic covalent bonds and application thereof
CN108341948A (en) A kind of hybrid cross-linked dynamic aggregation object and its application
CN107129580A (en) A kind of dynamic aggregation thing material and its application
CN108342002A (en) A kind of dynamic aggregation object and its application with hybrid cross-linked network
CN108341961B (en) Preparation and application of dynamic polymer containing combined dynamic covalent bonds
CN108342072A (en) A kind of dynamic aggregation object and its application with hybrid cross-linked structure
CN108342049A (en) A kind of physics split-phase dynamic aggregation object and its application
CN108341944A (en) A kind of energy-absorbing method based on dynamic aggregation object
CN109666167B (en) Hybrid dynamic polymer composition
CN108342037A (en) A kind of energy-absorbing method based on hybrid cross-linked network dynamic polymer
CN108341959A (en) A kind of dynamic aggregation object and its application
CN108342013A (en) A kind of hybrid cross-linked dynamic aggregation object and its application
CN109666178A (en) A kind of hydridization dynamic aggregation compositions and its application
CN109666159A (en) A kind of method of energy-absorbing and application thereof
CN109666153A (en) A kind of hydridization dynamic aggregation compositions and its application
CN109206825A (en) A kind of assembly energy-absorbing method based on physics split-phase supermolecule dynamic aggregation object
CN108341963A (en) A kind of dynamic aggregation object composition and its application with hybrid structure
CN108341955A (en) A kind of dynamic aggregation object or composition and its application with hydridization bonding structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20210309

Address after: Room 3162, Xuanye building, Pioneer Park, torch hi tech Zone, Xiamen, Fujian, 361000

Applicant after: Xiamen Daimeng Sports Technology Co.,Ltd.

Address before: 363000 room D, 15th floor, Huayuan Building, Yan'an North Road, dongputou street, Xiangcheng District, Zhangzhou City, Fujian Province

Applicant before: Weng Qiumei

WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20180731