CN108341960A

CN108341960A - It is a kind of to contain the dynamic aggregation object for combining dynamic covalent bond and its application

Info

Publication number: CN108341960A
Application number: CN201710055961.6A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Iron Cloth Mstar Technology Ltd
Priority date: 2017-01-25
Filing date: 2017-01-25
Publication date: 2018-07-31
Anticipated expiration: 2037-01-25
Also published as: CN108341960B

Abstract

A kind of dynamic aggregation object containing combination dynamic covalent bond, contains at least two class dynamic covalent bonds and optional hydrogen bond；Wherein, the dynamic covalent bond is organic boronic ester bond, is at least selected from organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key；The dynamic covalent bond exists as polymerization linking point and/or the crosslinking linking point of dynamic aggregation object, is the necessary condition to form or maintain dynamic aggregation object structure.The dynamic aggregation object can be used for making damping, buffering material, defense of resistance to impact material, energy-absorbing material, covering material, sound insulation deadener, intelligent-induction material, self-repair material, toughness material, force snesor etc..

Description

It is a kind of to contain the dynamic aggregation object for combining dynamic covalent bond and its application

Technical field

The present invention relates to a kind of dynamic aggregation object Material Fields, and in particular to a kind of to be gathered by what dynamic reversible covalent bond was constituted Close object material.

Background technology

Covalent type dynamic aggregation object is a uncharted field in polymer science research, the dynamic based on dynamic covalent bond Polymer had both had the molecular structure stabilized of traditional covalent polymer, possessed the dynamic of supermolecule polymer again under certain condition State invertibity is a kind of completely new intellectual material.Compared with the noncovalent interaction of supermolecule, the bond energy of dynamic covalent bond compared with By force, smaller by thermodynamic effects, being formed by dynamic aggregation object has more stable molecular structure, and dynamic covalent bond is well The invertibity of supermolecule noncovalent interaction and the stability of covalent bond are combined, functional molecular and material, exploitation are being constructed Novel energy-absorbing material, exploitation chemical sensor, regulation and control biomolecule, control smart molecule switch and machine etc. are shown Important function.

The covalent key class of dynamic found at present is more and more abundant, for being formed by dynamic aggregation by dynamic covalent bond The report of object is also more and more, is concentrated mainly in each dynamic aggregation object and contains only a kind of dynamic covalent bond to provide polymer Dynamic, but since the dynamic property of single dynamic covalent bond is limited, it is difficult to be formed and cooperate with orthogonal comprehensive performance.

Therefore, in order to obtain with diversity and cooperate with the dynamic aggregation object of orthogonal dynamic, need development a kind of new Dynamic covalent bond compositional model, it is insufficient to solve present in existing dynamic aggregation object.

Invention content

For above-mentioned background, the present invention relates to a kind of dynamic aggregation objects containing combination dynamic covalent bond, which is characterized in that It contains at least two class dynamic covalent bonds and optional hydrogen bond；Wherein, the dynamic covalent bond is organic boronic ester bond, choosing From but be not limited only to organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key；It is described Dynamic covalent bond exists as polymerization linking point and/or the crosslinking linking point of dynamic aggregation object, is to be formed or be maintained dynamic poly- The necessary condition of object structure is closed, the organic boronic ester bond and optional supermolecule hydrogen bond contained in dynamic aggregation object once solves From polymeric system is decomposed into following any or several secondary units：Monomer, polymer chain segment, polymer group Cluster etc.；Meanwhile organic boronic ester bond and optional supermolecule hydrogen bond can be passed through between dynamic aggregation object and above-mentioned secondary units Bonding and dissociation realize and mutually convert and dynamic reversible.The dynamic aggregation object or composition have excellent dynamic reversible Property, and reflect stimulating responsive, plasticity, self-repairability, recuperability, can the functional characteristics such as re-workability, while can To obtain good energy absorption capacity and toughness.

The present invention is achieved by following technical solution：

The present invention relates to a kind of dynamic aggregation objects containing combination dynamic covalent bond, which is characterized in that it contains at least two Class dynamic covalent bond and optional hydrogen bond；Wherein, the dynamic covalent bond is organic boronic ester bond, is selected from but is not limited only to Organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key；The dynamic covalent bond is made Exist for the polymerization linking point and/or crosslinking linking point of dynamic aggregation object, be to form or maintain dynamic aggregation object structure must Want condition.Polymer chain topological structure in the dynamic aggregation object and its composition and material composition is selected from line style, ring-type, branch Change, cluster, crosslinking and combinations thereof form.

A preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described is dynamic State polymer has non-crosslinking structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, all types of dynamics are total The sum of degree of cross linking of valence link is less than gel point.This structure is the simplest, is also convenient for being prepared into the material of the forms such as solution and cream, glue Material.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has non-crosslinking structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all dynamic covalent bonds The degree of cross linking in its gel point hereinafter, the degree of cross linking of supermolecule hydrogen bond in gel point hereinafter, and dynamic covalent bond and hydrogen bond friendship The sum of connection degree is less than gel point.It is simple in structure, and the introducing of supermolecule hydrogen bond, it can play and cooperate with orthogonal effect.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein all types of dynamic The degree of cross linking of state covalent bond is more than gel point.In this embodiment, as long as there is a kind of dynamic covalent bond to be maintained at gel Or more, you can the bridging property of guarantee system.The degree of cross linking of the system is higher, is conducive to the material for obtaining strong mechanical performance.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein at least a kind of dynamic The degree of cross linking of covalent bond is more than gel point, and the degree of cross linking of at least a kind of dynamic covalent bond is below gel point.The degree of cross linking is moderate, It is convenient that properties of product are regulated and controled as needed.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein all types of dynamic The degree of cross linking of state covalent bond in gel point hereinafter, but the sum of its degree of cross linking more than gel point.The degree of cross linking is relatively low, is also convenient for root According to needing to regulate and control properties of product.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition；Wherein, described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamics are covalent The degree of cross linking of key is more than gel point, and the degree of cross linking of hydrogen bond is more than gel point.In this embodiment, as long as having a kind of dynamic State covalent bond is maintained at gel point or more, you can the bridging property of guarantee system.The degree of cross linking is high, and contains a large amount of hydrogen bonds, convenient It obtains high strength and cooperates with orthogonal effect.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamics are covalent The degree of cross linking of key is more than gel point, and the degree of cross linking of hydrogen bond is below gel point.In this embodiment, as long as having a kind of dynamic State covalent bond is maintained at gel point or more, you can the bridging property of guarantee system.The degree of cross linking is higher, and hydrogen bond content is relatively low, Ke Yiqi To the supermolecule dynamic action of auxiliary.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein at least a kind of dynamic covalent bond The degree of cross linking more than gel point, the degree of cross linking of at least a kind of dynamic covalent bond is in gel point hereinafter, the degree of cross linking of hydrogen bond is solidifying It is more than glue point.The degree of cross linking is moderate, while introducing hydrogen bond, facilitates acquisition high resiliency, higher force intensity and cooperates with orthogonal effect.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamics are covalent The degree of cross linking of key is in gel point hereinafter, the degree of cross linking of hydrogen bond is more than gel point.The degree of cross linking is relatively low, convenient as needed to production Moral character can be regulated and controled, and the higher hydrogen bond of content provides for system and cooperates with orthogonal effect.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamics are covalent The degree of cross linking of key in gel point hereinafter, the degree of cross linking of hydrogen bond in gel point hereinafter, but dynamic covalent bond and hydrogen bond the degree of cross linking The sum of be not less than gel point.The degree of cross linking is relatively low, is also convenient for as needed regulating and controlling properties of product.

Another preferred embodiment according to the present invention provides a kind of dynamic aggregation object or its composition, wherein described Dynamic aggregation object has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein at least a kind of dynamic covalent bond The degree of cross linking more than gel point, the degree of cross linking of at least a kind of dynamic covalent bond is in gel point hereinafter, the degree of cross linking of hydrogen bond is solidifying Below glue point.The degree of cross linking is relatively low, convenient to regulate and control as needed to properties of product, exists simultaneously supermolecule hydrogen bond and provides auxiliary Supermolecule dynamic action.

The present invention can also have other embodiments, those skilled in the art can be with logic according to the present invention and train of thought Reasonably realize.

The organic boronic cyclic ester key in the present invention, can be selected from but be not limited only to such as at least one in lower structure Kind：

Wherein, a boron atom forms cyclic annular organic boronic ester units with two oxygen atoms simultaneously；Boron in the structure 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；It indicates to link or the connection of any other suitable group/atom with hydrogen atom, polymer chain, crosslinking, boron original Sub and at least one carbon atom is accessed by least one connection in polymer chain respectively；Difference on the same carbon atomCyclization can be connected, on different carbon atomsCyclization can also be connected, the ring can be selected from but be not limited only to fat The arbitrary combination of fat race ring, aromatic ring, ether ring, condensed ring, any of the above ring；Difference in the same boron atomIt can be with Connection is cyclic, in different boron atomsCan also connect cyclization, the ring can be selected from but be not limited only to aliphatic ring, The arbitrary combination of aromatic ring, ether ring, condensed ring, any of the above ring；L is linker, can also pass through atom/group on L Access in polymer chain, atom/group on L can also on the C of its both sidesConnection cyclization.

The organic boronic monoester bond in the present invention, can be selected from but be not limited only to such as at least one in lower structure Kind：

Wherein, the oxygen atom being connected by the atom in addition to the boron atom with two when single one boron atom difference Form hexatomic ring or hexatomic ring cyclic annular organic boronic ester units below；At least one carbon atom passes through boron carbon in the structure Key is connected with boron atom；Indicate with hydrogen atom, polymer chain, be crosslinked and link or any other suitable group/atom Connection, boron atom and at least one carbon atom are accessed by least one connection in polymer chain respectively；The same carbon is former Difference on sonCyclization can be connected, not by the connected different carbon atoms of single a boron atomIt can also Connection is cyclic, in different boron atomsCan also connect cyclization, the ring can be selected from but be not limited only to aliphatic ring, The arbitrary combination of aromatic ring, ether ring, condensed ring, any of the above ring；L₀For linker, wherein at least skeleton is former containing there are two Son can also pass through L₀On atom/group access polymer chain in, L₀On atom/group can also on the C of its both sidesConnection cyclization；L₁、L₂、L₃、L₄For linker, L can also be passed through₁、L₂、L₃、L₄On atom/group access polymer chain In, L₁、L₂、L₃、L₄On atom/group can also in its both sides carbon atom/boron atomConnection cyclization.

The organic boronic estersil key in the present invention, can be selected from but be not limited only to such as lower structure：

Wherein, a boric acid estersil key (B-O-Si) is at least formed between boron atom and silicon atom；In the structure at least It is connected with boron atom by boron carbon key there are one carbon atom, and at least one organic group is keyed to boron by the boron carbon On atom；Indicate with polymer chain, be crosslinked and link or the connection of any other suitable group/atom, boron atom and silicon Atom accesses polymer network by least one connection respectively.

The organic boronic acid anhydride key in the present invention, can be selected from but be not limited only to such as at least one of lower structure：

Wherein, a boric acid acid anhydride key (B-O-B) is at least formed between boron atom and boron atom；Each boron is former in the structure Son is at least 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；It indicates to link or the connection of any other suitable group/atom with polymer chain, crosslinking, at least two differences Boron atom pass through at least one connection respectively and access polymer network；In different boron atomsCyclization can be connected, The ring can be selected from but be not limited only to arbitrary, the combination of aliphatic ring, aromatic ring, ether ring, more than condensed ring several rings； L₃、L₄For linker, L can also be passed through₃、L₄On atom/group access polymer chain in, L₃、L₄On atom/group also may be used With in its both sides boron atomConnection cyclization.

Described in the present invention organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic Boric acid acid anhydride key by organic boronic primitive respectively with dihydroxy primitive, single hydrocarbon hydroxyl primitive, silicone hydroxyl/silicone hydroxyl presoma, organic Boric acid elementary reaction is formed.

The organic boronic primitive described in the present invention, may be selected from but not limited to organic boron acidic group, organic boronic ester group, Organic boronic alkali, organic boron alkylhalide group；

The dihydroxy primitive in the present invention, can be selected from but be not limited only to 1,2- glycol primitive, 1,3- glycol-baseds Member, adjacent two phenolic hydroxyl group primitives and 2- hydroxymethyl phenol hydroxyl primitives；

Single hydrocarbon hydroxyl primitive in the present invention can be selected from but be not limited only to containing single alkanol primitive, monoene alcohol radical Member, single phenol hydroxyl primitive, the polyphenol hydroxyl primitive in meta position, the polyphenol hydroxyl primitive in contraposition and interval at least four The polyhydroxy primitive of atom；

The silicone hydroxyl in the present invention, refers to a hydroxyl institute being connected by silicon atom and with the silicon atom The structural motif (Si-OH) of composition, wherein silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with one Carbon atom is connected by silicon-carbon bonds, and at least one organic group is keyed to by the silicon-carbon on silicon atom), or Inorganic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, A hydroxyl (- OH) in silicone hydroxyl is a functional group；

The silicone hydroxyl precursor in the present invention, refers to one be connected by silicon atom and with the silicon atom Hydrolyzable obtains the structural motif (Si-A) that the group of hydroxyl is formed, wherein A is that hydrolyzable obtains the group of hydroxyl, can Selected from halogen, cyano, oxygen cyano, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, Ketoxime base, alkoxide group.In the present invention, the group (- A) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is one Functional group.

In embodiments of the present invention, the optional supermolecule hydrogen bond action, by being present in dynamic aggregation object In chain backbone (including side chain/branch/bifurcated chain), side group, end group hydrogen bond is formed between the hydrogen bond group of one or more It constitutes.The hydrogen bond group preferably comprises following constituent：

At least one of further preferably following constituent：

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.

In embodiments of the present invention, rational formula combination can be carried out at least with following several compounds and is used as raw material Reaction obtains the dynamic aggregation object：

Organoboron compound (I) containing organic boronic primitive；Compound (II) containing dihydroxy primitive；Contain single hydrocarbon The compound (III) of hydroxyl primitive；Compound (IV) containing silicone hydroxyl/silicone hydroxyl precursor；Contain various hydroxyl bases simultaneously The compound (V) of at least one of member and organic boronic primitive；Contain the dynamic covalent bond and other reactive groups Compound (VI)；Without containing organic boronic primitive, various hydroxyl primitives and dynamic covalent bond but contain other reactive bases The compound (VII) of group.

Compound (I)~(VII) can be the micromolecular compound that molecular weight is no more than 1000Da, also may be used To be macromolecular compound of the molecular weight more than 1000Da；Organoboron compound (I), compound (II), compound (III), In compound (IV), compound (V), it can contain or not contain other reactive groups.

The present invention provides a kind of preparation method of the dynamic aggregation object containing combination dynamic covalent bond, the dynamic aggregation Object contains line style or cyclic structure, preferably prepared by least one of following methods (but the present invention is unlimited In this)：

The first, participates in reaction by least following components and generates the acquisition of dynamic covalent bond key：At least one organoboration Object (I) is closed, at least two hydroxy-containing compounds (are selected from compound (I), compound (II)~compound containing organic boronate (IV), similarly hereinafter)；Wherein, organoboron compound (I), hydroxy-containing compounds contain at most Liang Ge functional groups；

Second, reaction is participated in by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one Kind organoboron compound (I), at least two hydroxy-containing compounds；Or at least one organoboron compound (I), at least two are containing hydroxyl The combination of based compound and at least one compound (VII)；Wherein, organoboron compound (I) and hydroxy-containing compounds contain One functional group and other reactive groups, compound (VII) contain at most two other reactive groups；

The third, participates in reaction by least following components and generates the acquisition of dynamic covalent bond：At least one compound (V), Or itself and at least one organoboron compound (I) or at least two hydroxy-containing compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), organoboron compound (I), hydroxy-containing compounds contain At most Liang Ge functional groups.

4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (VI), Or itself and at least one compound (VII)；Wherein, two class dynamic covalent bonds, compound are at least contained in compound (VI) (VI), compound (VII) contains at most two other reactive groups.

The present invention provides a kind of preparation method of the dynamic aggregation object based on combination dynamic covalent bond, the dynamic aggregation Object has branched structure, is preferably prepared (however, the present invention is not limited thereto) by least one of following methods：

The first, participates in reaction by least following components and generates the acquisition of dynamic covalent bond key：At least one organoboration Close object (I), at least two hydroxy-containing compounds；Wherein, at least one chemical combination in organoboron compound (I), hydroxy-containing compounds Object contains at least three functional groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more；

Second, reaction is participated in by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one Kind organoboron compound (I), at least two hydroxy-containing compounds；Wherein, in organoboron compound (I) and hydroxy-containing compounds extremely A few compound contains at least one functional group and at least one other reactive group and functional group and other reactive bases The sum of group's number no less than three, and a combination thereof does not generate the common covalent cross-linking of gel point or more；

The third, participates in reaction by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one Kind compound (V), at least one compound (VII) or this two, at least one organoboron compound (I) or at least two Kind hydroxy-containing compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), organoboron compound (I), hydroxy-containing compounds containing at most Liang Ge functional groups and at least one compound (V) or have Machine boron compound (I) or hydroxy-containing compounds contain at least one other reactive group, and a combination thereof does not generate gel point Above common covalent cross-linking.

4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (VI), Or itself and at least one compound (VII)；Wherein, two class dynamic covalent bonds are at least contained in compound (VI), it is at least one Compound (VI) or at least one compound (VII) contain at least three other reactive groups, and a combination thereof do not generate it is solidifying Common covalent cross-linking more than glue point.

The present invention provides a kind of preparation method of the dynamic aggregation object based on combination dynamic covalent bond, the dynamic aggregation Object has dynamic crosslinking structure, preferably prepared by least one of following methods (but the present invention is not limited to This)：

The first, participates in reaction by least following components and generates the acquisition of dynamic covalent bond：At least one organic boron chemical combination Object (I), at least two hydroxy-containing compounds；Wherein, organoboron compound (I) and hydroxy-containing compounds contain at least two functions Group, and at least one organoboron compound (I) or at least one hydroxy-containing compounds contain at least three functional groups, and its group Close the common covalent cross-linking for not generating gel point or more；

Second, reaction is participated in by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one Kind organoboron compound (I), at least two hydroxy-containing compounds；Wherein, organoboron compound (I) and hydroxy-containing compounds contain Functional group and the sum of other reactive group numbers no less than two, and at least one organoboron compound (I) or at least one contain The sum of functional group that hydroxy compounds contains and other reactive group numbers no less than three, and a combination thereof do not generate gel point with On common covalent cross-linking；

The third, participates in reaction by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one It plants compound (V) or it contains at least one compound (VII) or at least one organoboron compound (I) or at least two Hydroxy compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), have Machine boron compound (I), hydroxy-containing compounds contain at least two functional groups, and at least one compound (V) or organoboration It closes object (I) or hydroxy-containing compounds contains at least three functional groups, or at least one compound (V) or organoboron compound (I) or hydroxy-containing compounds contain at least one other reactive group, and a combination thereof does not generate the common of gel point or more Covalent cross-linking；

4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (VI), Or itself and at least one compound (VII)；Wherein, two class dynamic covalent bonds, compound are at least contained in compound (VI) (VI), compound (VII) contains at least two other reactive groups, and at least one compound (VI) or at least oneization It closes object (VII) and contains at least three other reactive groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more.

In the present invention, since the preparation process step for preparing dynamic aggregation object using above-mentioned several embodiments is simple, Operation is easy, and controllability is strong, therefore is the preferred embodiment of the present invention.

The present invention also provides a kind of energy-absorbing methods, which is characterized in that provides a kind of dynamic containing combination dynamic covalent bond Polymer, and energy-absorbing is carried out using it as energy-absorbing material, contain at least two class dynamic covalent bonds and optional hydrogen bond；Wherein, The dynamic covalent bond be organic boronic ester bond, be selected from but be not limited only to organic boronic cyclic ester key, organic boronic monoester bond, Organic boronic estersil key and organic boronic acid anhydride key；The dynamic covalent bond as dynamic aggregation object polymerization linking point and/or It is crosslinked linking point and exists, be the necessary condition to form or maintain dynamic aggregation object structure, what is contained in dynamic aggregation object is organic Once dissociating, polymeric system is decomposed into following any or appoints several times for boric acid ester bond and optional supermolecule hydrogen bond Grade unit：Monomer, polymer chain segment, polymer cluster etc.；Meanwhile it can pass through between dynamic aggregation object and above-mentioned secondary units The bonding of organic boronic ester bond and optional supermolecule hydrogen bond and dissociation, which are realized, to be mutually converted and dynamic reversible.

In embodiments of the present invention, the dynamic aggregation object form containing combination dynamic covalent bond key can be molten Liquid, lotion, cream, glue, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer Swell gel, ionic liquid swell gel), foam etc..

In embodiments of the present invention, property is also an option that in preparation process certain add is added in dynamic aggregation object The other polymers that add, auxiliary agent, filler are blended to collectively constitute dynamic aggregation object.

In embodiments of the present invention, the dynamic aggregation object or its component property are adjustable on a large scale, navigate in military affairs The fields such as its equipment, functional coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material all have wide Wealthy application prospect.Specifically, it can be applied to and make damper, energy-absorbing material, padded coaming, defense of resistance to impact material Material, athletic protective article, army and police's protective article, force snesor, self-repairability coating, self-repairability plank, self-repairability bond The products such as agent, bulletproof glass squeegee, toughness material, sound insulation deadener, shape-memory material, sealing element, toy.

Compared with prior art, the invention has the advantages that：

(1) in dynamic aggregation object of the invention, at least contain two classes dynamic covalently organic boronic ester bond, it is different types of dynamic Intensity, structure, dynamic, response and the formation condition of the covalent organic boronic ester bond of state etc. are different, can reach collaboration The orthogonal impact of performance again；Also, it can be exchanged with each other and convert between each organic boronic ester bond under certain condition, make material Structure and performance have more adjustability.

(2) in dynamic aggregation object of the invention, also optionally contain hydrogen bond.Containing at least two class organic boronic ester bonds On the basis of, hydrogen bond action is added, a wide range of adjustable performance such as intensity, dynamic and response can be obtained；Meanwhile may be used also With easily regulate and control the hydrogen bond of introducing quantity and its with the link structure of polymer chain, to obtain hydrogen bond and glass transition The controllable dynamic aggregation object of temperature.Covalently organic boronic ester bond and hydrogen bond under external force can be with " can sacrifice key " for dynamic Form be broken, on the one hand can dissipate a large amount of energy, can be provided for cross-linked polymer in specific structure excellent Different tensile toughness and tear resistance；On the other hand super stretching percentage of elongation can be obtained；Due to the covalent organic boric acid ester of dynamic The intensity of key is usually than hydrogen bond higher, when being destroyed by external force, hydrogen bond and organic boronic ester bond can with the variation of genetic sequence, Hydrogen bond generally first dissociates, and to generate the dissipation step by step to power, is conducive to the tolerance for improving material to external force.In addition, Dynamic based on organic boronic ester bond and hydrogen bond can also obtain the self-repairability of orthogonality, plasticity, can re-workability.

(3) dynamic response of organic boronic ester bond is strong in dynamic aggregation object, dynamic response mild condition.Compared to existing Other dynamic covalent systems, the present invention take full advantage of organic boronic ester bond with good thermal stability and high dynamic Invertibity, can without catalyst, without high temperature, illumination or specific pH under conditions of realize dynamic aggregation object synthesis and dynamic Invertibity also reduces the limitation of use environment while improving preparation efficiency, and extend polymer applies model It encloses.In addition, by optionally controlling other conditions (auxiliary agent, adjustment reaction temperature is such as added), it can be in ring appropriate Under border, accelerates or be quenched dynamic covalent chemical balance, be at required state, this is in existing supramolecular chemistry and moves It is more difficult inside state covalent systems to accomplish.

It (4) in the present invention, can using the dynamic of organic boronic ester bond in dynamic aggregation object and optional supermolecule hydrogen bond Inverse property, when by external impacts, on the one hand polymer can show thickening response, on the other hand can also pass through organic boron The reversible fracture of acid esters key and hydrogen bond reaches multi-absorption and the dissipation to impact energy.For non-crosslinked system, thickening response Complete viscous loss enhancing is generated, strong energy absorption is played；And for dynamic crosslinking system, then it can generate viscosity- Elasticity transformation, can reduce the destruction of material while viscous loss.

With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.

Specific implementation mode

The present invention relates to a kind of dynamic aggregation objects containing combination dynamic covalent bond, which is characterized in that it contains at least two Class dynamic covalent bond and optional hydrogen bond；Wherein, the dynamic covalent bond is organic boronic ester bond, is selected from but is not limited only to Organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key；The dynamic covalent bond is made Exist for the polymerization linking point and/or crosslinking linking point of dynamic aggregation object, be to form or maintain dynamic aggregation object structure must Condition is wanted, the organic boronic ester bond and optional supermolecule hydrogen bond contained in dynamic aggregation object once dissociates, polymeric system It is decomposed into following any or several secondary units：Monomer, polymer chain segment, polymer cluster etc.；Meanwhile dynamic It can be real by the bonding and dissociation of organic boronic ester bond and optional supermolecule hydrogen bond between polymer and above-mentioned secondary units It now mutually converts and dynamic reversible.The dynamic aggregation object or composition have excellent dynamic reversibility, and reflect thorn Swash response, plasticity, self-repairability, recuperability, can the functional characteristics such as re-workability, while good energy-absorbing can be obtained Property and toughness.

Term " polymerization " reaction/action used in the present invention is propagation process/effect of chain, refers to lower molecular weight Reactant pass through the reaction formations such as polycondensation, addition polymerization, ring-opening polymerisation synthesis with higher molecular weight product process.This its In, reactant, which is typically polymerizing power, (can spontaneously be polymerize, or can add in initiator or outside and can act on It is lower to be polymerize) the compounds such as monomer, oligomer, prepolymer.It is referred to as equal by a kind of product that reactant is polymerize Polymers.The product being polymerize by two or more reactant is known as copolymer.It should be pointed out that in the present invention Described in " polymerization ", it includes the linear growth process of reactant molecule chain, include the branched process of reactant molecule chain, packet The annulation process of the chain containing reactant molecule, also includes the cross-linking process of reactant molecule chain.In embodiments of the present invention, " polymerization " also includes chain growth caused by supermolecule hydrogen bond action.

Term " crosslinking " reaction/action used in the present invention refers to leading between reactant molecule and/or in reactant molecule Cross the chemistry of dynamic covalent bond and/or supermolecule hydrogen bond and/or supramolecular chemistry connect to be formed with two dimension, three-dimensional cluster type into And form the process of three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is general first continuous in two-dimensional/three-dimensional direction Increase, gradually forms cluster (can be two dimension or three-dimensional), developing deeply is three-dimensional infinite network.Unless stated otherwise, this hair Crosslinking (structure) in bright only includes the three-dimensional infinite network (structure) of gel point or more (including gel point, similarly hereinafter), non-crosslinked (structure) then refers in particular to the structures such as gel point line style below, ring-type, branched and two dimension, three-dimensional cluster structure.

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 Join reaction product, there is three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer architecture, hand over It is relatively stable and secured to be coupled structure；It is only loose link structure in gel point cross-linking reaction product below, not shape At three-dimensional infinite network structure, a small amount of two dimension or three-dimensional net structure only are being locally lain in, and is being not belonging to across entire polymerization The cross-linked network that can constitute an entirety of object structure.

Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key is formed by a kind of interaction between atom by share electron pair, and (100 DEG C are generally not more than) under typical temperature More difficult be broken with (be generally less than 1 day) in the usual time comprising but be not limited only to common carbon-carbon bond, carbon-oxygen bond, Carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen key, nitrogen-nitrogen key etc..

The dynamic aggregation object, polymer chain topological structure can be selected from line style, ring-type, branched, cluster, crosslinking and its Combining form；Its form and the chain topological structure of polymer in raw material also can be selected from line style, ring-type, branched, cluster, crosslinking and A combination thereof form.

Wherein, described " line style " structure, refer to polymer molecular chain presentation is rule or irregular long chain line Shape is generally formed by connecting by many repetitive units on a continuous length, and the side group in polymer molecular chain is not generally with branch Chain exists；It is usually that polycondensation reaction, sudden reaction or open loop are passed through by the monomer without long-chain side group for " linear structure " The polymerizations such as reaction are formed.

Wherein, described " ring-type " structure, refers to that polymer molecular chain exists in the form of closed chain comprising single The cyclic structure of the forms such as ring, polycyclic, bridged ring, nested rings；For cyclic structure, line style or branched polymer can be passed through Intramolecular and/or intermolecular cyclization are formed, and can also be prepared by the methods of ring expansion polymerization reaction.

Wherein, described " branched " structure refers on polymer molecular chain containing knots such as side chain, branch and bifurcated chains Structure includes but are not limited to the structures such as star-like, H-type, combed, dendritic, hyperbranched and combinations thereof and itself and line style, ring-type Structure is further combined, such as line style chain end connection ring shape structure, cyclic structure are combined with comb-type structure, dendritic last-in-chain(LIC) End connection endless chain, etc.；For structures such as the side chain of polymer, branch and bifurcated chains, there can be a multilevel hierarchy, such as It can continue to carry one or more levels branch on the branch of polymer molecular chain.For " branched structure ", preparation method is many, It is generally well known to those skilled in the art, such as polycondensation reaction can be carried out by the monomer containing long-chain side group and formed, or Person is formed in addition polymerization process by the chain transfer reaction of free radical, or by radiating and chemically reacting on line style strand Extend branched structure to be formed.Branched structure, which further carries out intramolecular and/or intermolecular reaction (crosslinking), can generate cluster And cross-linked structure.

Wherein, described " cluster " structure refers to that polymer chain carries out intramolecular and/or intermolecular reaction and generates Gel point two-dimensional/three-dimensional structure below.

Wherein, described " crosslinking " structure, spy refer to the three-dimensional infinite network structure that polymer has.

In embodiments of the present invention, can only have one in the dynamic aggregation object and its composition and material composition The polymer of kind topographic morphologies can also be the mixture of the polymer there are many topographic morphologies.

The dynamic aggregation object can contain dynamic covalent bond on any appropriate position of polymer.For Noncrosslinking dynamic aggregation object can contain dynamic covalent bond on the arbitrary chain backbone of polymer；For crosslinked dynamic aggregation Object can contain dynamic covalent bond on the arbitrary chain backbone of polymer；The present invention be also not precluded within polymer chain side group and/or Contain dynamic covalent bond on end group；Wherein, dynamic covalent bond is contained preferably on polymer chain skeleton.The dynamic covalent bond In general, reversible fracture and regeneration can be carried out；Under suitable conditions, in dynamic aggregation object any position it is dynamic State covalent bond can participate in dynamic reversible exchange.

In the present invention, the polymer chain skeleton refers to being present in the arbitrary segment in polymer network structure The polymer chain bone in cross-linked network chain and its side chain, branch, bifurcated chain and non-crosslinking structure in skeleton, including cross-linked structure Frame and its side chain, branch, bifurcated chain.

In the present invention, " side chain " refers to being connected with polymeric chain backbone and being distributed in polymer architecture It is more than the chain structure of 1000Da in the molecular weight of its skeleton side；Wherein, the branch, bifurcated chain are referred to from polymer chain The molecular weight that skeleton or any other chain bifurcated come out is more than the chain structure of 1000Da；For the sake of simplicity, side chain, branch, bifurcated When the molecular weight of chain is more than 1000Da, if not otherwise indicated, then it is collectively referred to as side chain.Wherein, " side group ", refers to The molecular weight for being connected with polymer chain skeleton in polymer architecture and being distributed in chain backbone side is not higher than the chemistry of 1000Da Group and molecular weight are not higher than the short-side chain of 1000Da.For side chain and side group, can have multilevel hierarchy namely side chain can be with Continue to carry side group and side chain, the side chain of side chain can continue have side group and side chain, and side chain therein also includes branch and bifurcated Chain isodesmic structure.Wherein, " end group " refers to being connected with polymer chain skeleton in polymer architecture and being located at chain The chemical group of skeleton end；In the present invention, side group can also have end group under specific condition.

In the present invention, contain at least two class dynamic covalent bonds in the dynamic aggregation object namely it is selected from but not only limits At least two classes in organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key, because This contains combination dynamic covalent bond structure；At the same time it can also contain optional hydrogen bond.The dynamic aggregation object or its composition can be with Regulated and controled by chemical constitution, topological structure, constituent, form etc., obtains ideal performance.

In the present invention, described at least two class dynamic covalent bonds can be on same polymer, can also be in difference Polymer；The dynamic covalent bond and optional hydrogen bond group can be on same polymer, can also be different On polymer.When different dynamic covalent bond or dynamic covalent bond from hydrogen bond group on different polymer when, the dynamic Polymer is a kind of polymer composition；Wherein, hydrogen bond group also is present in small molecule and filler.

In the present invention, when there are multiple component of polymer, each ingredient can be mutually perhaps incompatible；When in the presence of at least one It when the crosslinked ingredient of kind, can mutually disperse between heterogeneity, is mutually interspersed or partly interspersed, but the present invention is not limited only to This.

In embodiments of the present invention, the optional supermolecule hydrogen bond action, can be by being present in dynamic aggregation Appoint the hydrogen of one or more in polymer chain skeleton (including side chain/branch/bifurcated chain), side group, end group in object and its composition Hydrogen bond is formed between key group to constitute.Wherein, the hydrogen bond group can also simultaneously or exist only in dynamic aggregation object composition In other compositions in, the other compositions include but are not limited to small molecule, polymer, filler.

In the present invention, when the dynamic of dynamic covalent bond and supermolecule hydrogen bond is sufficiently strong, if its respective degree of cross linking And its sum of in gel point hereinafter, when dilatant behaviour then occurs, be easy to generate the promotion of viscosity, increase viscous loss；If its One of the degree of cross linking is more than gel point or the sum of its degree of cross linking is more than gel point, then when dilatant behaviour occurs, be easy to generate The transformation of visco-elastic.Therefore, crosslinking has their own characteristics each with non-crosslinked, and those skilled in the art can be based on application scenario and want It asks and is reasonably designed and be achieved.The organic boronic cyclic ester key in the present invention, can be selected from as in lower structure At least one：

Wherein, a boron atom forms cyclic annular organic boronic ester units with two oxygen atoms simultaneously；Boron in the structure 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；It indicates to link or the connection of any other suitable group/atom with hydrogen atom, polymer chain, crosslinking, boron original Sub and at least one carbon atom is accessed by least one connection in polymer chain respectively；Difference on the same carbon atomCyclization can be connected, on different carbon atomsCyclization can also be connected, the ring can be selected from but be not limited only to fat The arbitrary combination of fat race ring, aromatic ring, ether ring, condensed ring, any of the above ring；Difference in the same boron atomIt can be with Connection is cyclic, in different boron atomsCan also connect cyclization, the ring can be selected from but be not limited only to aliphatic ring, The arbitrary combination of aromatic ring, ether ring, condensed ring, any of the above ring；Wherein, L is linker, may include carbon atom and oxygen, The hetero atoms such as nitrogen, sulphur connect the nearest skeletal atom number no more than 3 of two hydroxyls and do not form a diphenol；Original on L Son/group can also on its both sides carbon atomConnection cyclization.

In the present invention, the organic boronic cyclic ester key is preferably by by organic boronic primitive and dihydroxy elementary reaction It generates.The dihydroxy primitive can be selected from but be not limited only to 1,2- glycol primitive, 1,3- glycol primitive, adjacent two phenolic hydroxyl groups Primitive, 2- hydroxymethyl phenol hydroxyl primitives；

Wherein, 1, the 2- glycol primitives, can be selected from glycol moleculeIt is former to lose at least one non-hydroxyl hydrogen The residue formed after son；

Wherein, 1, the 3- glycol primitives, can be selected from 1,3-PD moleculeIt loses at least one non- The residue formed after hydroxyl hydrogen atom；

Wherein, adjacent two phenolic hydroxyl group primitives its can be selected from being formed after adjacent diphenol loses non-hydroxyl hydrogen atom at least one aromatic ring Residue, miscellaneous adjacent diphenol lose the residue formed after the non-hydroxyl atom at least one heteroaromatic；

Wherein, 2- hydroxymethyl phenols hydroxyl primitive its can be selected from 2- hydroxymethyl phenols, 2- methylol creosotes lose it is at least one non- The residue formed after hydroxyl hydrogen atom.

In the present invention, the organic boronic monoester bond, can be selected from such as at least one of lower structure：

The organic boronic monoester bond is preferably given birth to by organic boronic primitive and single hydrocarbon hydroxyl elementary reaction in the present invention At single hydrocarbon hydroxyl primitive may be selected from but not limited to single alkanol hydroxyl primitive, monoene alcoholic extract hydroxyl group primitive, single phenol hydroxyl In primitive, at least four atom polyols of the polyphenol hydroxyl in meta position, the polyphenol hydroxyl in contraposition and interval Hydroxyl；

Wherein, single alkanol hydroxyl primitive refers to the carbon atom that hydroxyl is directly connected to being that alkyl carbon is former Son includes the alkane of hetero atom connection；The monoene alcoholic extract hydroxyl group primitive, refer to be with the carbon atom that hydroxyl is directly connected to Ethylenic unsaturation alkyl carbon atom includes the alkene of hetero atom connection；The single phenol hydroxyl primitive, refers to direct with hydroxyl The carbon atom of connection is aromatic hydrocarbon carbon atom, including miscellaneous aromatic hydrocarbon；If there are two or more single hydrocarbon hydroxyls in compound Base primitive at least can be then at least four atoms of the polyphenol hydroxyl in meta position, the polyphenol hydroxyl in contraposition and interval Hydroxyl in polyol.

The organic boronic estersil key in the present invention, with structure as follows：

Wherein, the silicone hydroxyl refers to that a hydroxyl being connected by silicon atom and with the silicon atom is formed Structural motif (Si-OH), wherein silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with a carbon original Son is connected by silicon-carbon bonds, and at least one organic group is keyed to by the silicon-carbon on silicon atom) or it is inorganic Silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, silicon hydroxyl A hydroxyl (- OH) in base is a functional group.

Wherein, the silicone hydroxyl precursor, refer to one be connected by silicon atom and with the silicon atom can water Solution obtains the structural motif (Si-A) that the group of hydroxyl is formed, wherein A is that hydrolyzable obtains the group of hydroxyl, be 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.In the present invention, the group (- A) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is a function Group.

The organic boronic acid anhydride key in the present invention, can be formed by suitable organic boronic elementary reaction, It can be selected from such as at least one of lower structure：

Wherein, a boric acid acid anhydride key (B-O-B) is at least formed between boron atom and boron atom；Each boron is former in the structure Son is at least 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；It indicates to link or the connection of any other suitable group/atom with polymer chain, crosslinking, at least two differences Boron atom pass through at least one connection respectively and access polymer network；In different boron atomsCyclization can be connected, The ring can be selected from but be not limited only to the arbitrary combination of aliphatic ring, aromatic ring, ether ring, condensed ring, any of the above ring； L₃、L₄For linker, L can also be passed through₃、L₄On atom/group access polymer chain in, L₃、L₄On atom/group also may be used With in its both sides boron atomConnection cyclization.

The organic boronic primitive in the present invention, can be selected from but be not limited only to organic boron acidic group, organic boric acid ester At least one of base, organic boronic alkali, organic boron alkylhalide group.

In embodiments of the present invention, the organic boron acidic group, refer to by boron atom and with the boron atom The structural motif (B-OH) that connected at least one hydroxyl is formed, and boron atom therein at least passes through boron with a carbon atom Carbon key is connected, and at least one organic group is keyed to by the boron carbon in boron atom.

In embodiments of the present invention, the organic boronic ester group refers to being connected by boron atom, with the boron atom At least one oxygen atom and the alkyl or silylation that are connected with the oxygen atom formed structural motif (B-OR, wherein R be with Alkyl based on carbon, hydrogen atom or the silylation based on silicon, hydrogen atom pass through carbon atom or silicon atom and oxygen atom phase Even), and boron atom therein is at least connected with a carbon atom by boron carbon key, and at least one organic group is described in Boron carbon is keyed in boron atom.

In embodiments of the present invention, the organic boronic alkali refers to including at least in compound structure Structural motif (the B-O that one at least one negative oxygen ion being connected by boron atom and with the boron atom is formed^-) and at least Including a cation (Mⁿ⁺), and boron atom therein is at least connected with a carbon atom by boron carbon key, and at least one Organic group is keyed to by the boron carbon in boron atom.

In embodiments of the present invention, the organic boron alkylhalide group, refer to by boron atom and with the boron original The structural motif (B-F, B-Cl, B-Br, B-I) that the connected at least one halogen atom (F, Cl, Br, I) of son is formed, and wherein Boron atom be at least connected by boron carbon key with a carbon atom, and at least one organic group is keyed by the boron carbon Onto boron atom.

The optional supermolecule hydrogen bond action in the present invention is surpassed by any appropriate by what hydrogen bond was established Molecular action, the hydrogen atom being covalently attached to generally by the atom Z big with electronegativity and the atom that electronegativity is big, radius is small Y, using hydrogen as medium, generates the hydrogen bond link of Z-H ... Y shape formulas, wherein described Z, the Y is negative for any appropriate electricity between Z and Y Property big and atom that radius is small, can be same element may be not same element, can be selected from F, N, O, C, S, Cl, P, The atoms such as Br, I, more preferably F, N, O atom, more preferably O, N atom.Wherein, the supermolecule hydrogen bond action can be made For supermolecule polymerize and/or be crosslinked and/or chain in ring formation exist namely hydrogen bond can only play connection two or two with Cochain segment unit, which plays to increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond, only plays the friendship of interchain supermolecule Connection, or only play in chain two or more arbitrary combination in ring formation or three of the above.The present invention is also not excluded for Hydrogen bond plays the role of grafting.

In embodiments of the present invention, the hydrogen bond can be optional tooth number.Wherein, the number of teeth refer to by The donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group are formed by Hydrogen bond quantity, each H ... Y are combined as a tooth.In following formula, the hydrogen of a schematically illustrate tooth, two teeth and three tooth hydrogen bond groups is distinguished Key bonding situation：

The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows：

The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is with regard to weak, Ke Yiqi To the effect for promoting dynamic aggregation object to keep balanced structure and raising mechanical property (modulus and intensity).If the number of teeth of hydrogen bond Few, then intensity is low, and the dynamic of hydrogen bond action can provide dynamic property with regard to strong together with dynamic covalently organic boronic ester bond. In embodiments of the present invention, the preferably more than hydrogen bond action of four teeth.

In embodiments of the present invention, the supermolecule hydrogen bond action can be by between any appropriate hydrogen bond group Existing noncovalent interaction generates.Wherein, the hydrogen bond group can only contain hydrogen bond donor, or only contain hydrogen bond by Body, or contain hydrogen bond donor and receptor simultaneously, preferably contain hydrogen bond donor and receptor simultaneously.Wherein, the hydrogen bond group is excellent Choosing contains following constituent：

At least one of further preferably following constituent：

Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.In embodiments of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, thio ammonia The derivative etc. of carbamate base and the above group.

In the present invention, the hydrogen bond group can be only present on polymer chain skeleton (including side chain/branch/point Fork chain), referred to as skeleton hydrogen bond group；Polymer chain side group (multilevel hierarchy for also including side group) can also be existed only in, referred to as Side group hydrogen bond group；It can also exist only on polymer chain/small molecule end group, referred to as end group hydrogen bond group；It can also be simultaneously On being present at least two in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group.When existing simultaneously In polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group at least two on when, under specific circumstances, Hydrogen bond can be formed between the hydrogen bond group of different location, such as skeleton hydrogen bond group can form hydrogen between the hydrogen bond group of side Key.

Wherein, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this)：

Wherein, suitable side group hydrogen bond group/end group hydrogen bond group be in addition to can have above-mentioned skeleton 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 values, can also be average value, preferably smaller than 20, it is more excellent Choosing is less than 5.

In the present invention, one or more kinds of hydrogen bond groups can be contained in same dynamic aggregation object.Described Hydrogen bond group can be formed by any appropriate chemical reaction, such as：By carboxyl, acyl halide group, anhydride group, ester group, Covalent reaction between amide groups, isocyanate groups and amino is formed；Pass through isocyanate groups and hydroxyl, sulfydryl, carboxyl Between covalent reaction formed；It is formed by the covalent reaction between succinimide ester groups and amino, hydroxyl, sulfydryl.

In the present invention, the supermolecule hydrogen bond action can be the process into Mobile state covalent cross-linking in dynamic aggregation object Middle generation；Can also be to be generated in advance after supermolecule hydrogen bond action again into Mobile state covalent cross-linking；It can also covalently be handed in dynamic After connection is formed, supermolecule hydrogen bond action is generated during dynamic aggregation object subsequent forming, but the present invention is not limited only to this.

In the present invention, due to the intensity of different types of organic boronic ester bond and dynamic difference, different hydrogen bond knots Its performance of structure is also different, on the basis of containing at least two class organic boronic ester bond, adds hydrogen bond action, can obtain The a wide range of adjustable performance such as intensity, dynamic and response；At the same time it can also easily regulate and control introducing hydrogen bond quantity and The link structure of itself and polymer chain, to obtain the controllable dynamic aggregation object of hydrogen bond and glass transition temperature.Dynamic is altogether Valence organic boronic ester bond and hydrogen bond can be broken in the form of " can sacrifice key " under external force, on the one hand can be dissipated A large amount of energy can provide excellent tensile toughness and tear resistance in specific structure for cross-linked polymer；Another party Face can obtain super stretching percentage of elongation；Since the intensity of the covalent organic boronic ester bond of dynamic is usually than hydrogen bond higher, by outer When power is destroyed, hydrogen bond and organic boronic ester bond generally can first be dissociated with the variation of genetic sequence, hydrogen bond, to generation pair The dissipation step by step of power is conducive to the tolerance for improving material to external force.In addition, the dynamic aggregation object of the present invention is based on organic boronic The dynamic of ester bond and hydrogen bond can also obtain the self-repairability of orthogonality, plasticity, can re-workability.

Organoboron compound (I) containing organic boronic primitive；Compound (II) containing dihydroxy primitive；Contain single hydrocarbon The compound (III) of hydroxyl primitive；Compound (IV) containing silicone hydroxyl/silicone hydroxyl precursor；Contain various hydroxyl bases simultaneously The compound (V) of at least one of member and organic boronic primitive；Contain the dynamic covalent bond and other reactive groups Compound (VI)；Without containing organic boronic primitive, various hydroxyl primitives and dynamic covalent bond but contain other reactive groups Compound (VII).

Other described reactive groups, refer to can spontaneously or can in initiator or light, heat, irradiate, urge The group that chemical reaction generates common covalent bond is carried out under the conditions of change etc., suitable group includes but are not limited to：Carboxyl, carbonyl Base, 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, Malaysia Imide group, succinimide ester groups, norbornene group, azo group, azido group, heterocyclic group, triazoline two Ketone, carbon radicals, oxygen radical etc.；It is preferred that amino, sulfydryl, alkenyl, isocyanate groups, epoxy group, acrylate group, Acrylamide group.

Other described reactive groups in the present invention, play the role of in system, first, performing the derivatization anti- Hydrogen bond group should be prepared, second is that described compound itself or its between other compounds or react with it straight between product The reaction for connecting other reactive groups forms common covalent bond, so that the compound and/or its reaction The molecular weight increase of product/degree of functionality increases.

In embodiments of the present invention, described in the organoboron compound (I) containing organic boronic primitive Organic boron acidic group can be selected from but be not limited only to following any or appoint several structures：

Wherein, K₁For the group/atom being connected directly with boron atom, it is selected from following any structure：Hydrogen atom, miscellaneous original Subbase group, fatty oxyl, fragrant oxyl, small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are more than 1000Da Polymer chain residue；Work as K₁For fatty oxyl or fragrant oxyl when, organoboron compound (I) contains organic boronic simultaneously Base and organic boronic ester group, this helps to regulate and control the parameters such as its dissolubility, reaction rate, the extent of reaction, and can be used for regulating and controlling The performances such as the dynamic of dynamic aggregation object.Wherein, the cyclic structure in B4 is to contain the non-aromatic of at least one organic boron acidic group Property or armaticity boron heterocyclic group, boron atom be placed in cyclic structure, cyclic structure can be small molecule ring, can also be big point Subring is preferably 3~100 membered rings, more preferably 3~50 membered rings, more preferably 3~10 membered rings；Cyclic structure in B4 Ring member nitrogen atoms are each independently carbon atom, boron atom or other hetero atoms, and at least one ring member nitrogen atoms are boron atom and structure At organic boron acidic group, and at least one ring member nitrogen atoms and compound other atoms are connected；The each cyclization of cyclic structure in B4 is former Hydrogen atom on son can be substituted, and can not also be substituted；Cyclic structure in B4 can be single ring architecture, multiring structure, Spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；The connection of other atoms of expression with compound；It is described various Boron atom in structure is at least connected with a carbon atom by boron carbon key, and at least one organic group passes through the boron carbon It is keyed in boron atom.

Wherein, the cyclic structure in B4 can be selected from by it is any in the following group, any it is unsaturated in the form of, any quilt It is substitution form, any by hydridization form：The miscellaneous luxuriant and rich with fragrance, boron of boron heterocycle alkane, boron heterocyclic hydrocarbon, the miscellaneous benzene of boron, the miscellaneous naphthalene of boron, the miscellaneous anthracene of boron, boron Heteroaryl hydrocarbon；The preferred boron heterocycle pentane of listed cyclic structure, boron azacyclohexane, boron heterocycle hexene, boron heterocycle hexadiene, boron heterocycle The miscellaneous benzene of hexenone, boron.Citing is such as：

In embodiments of the present invention, when in the organoboron compound (I) contain two or more structures When primitive, connection structure L can be passed through₃、L₄It interconnects；When only there are one the structural motif when, can be connected to not Cyclization or not at any position of the polymer chain polymer chain of cluster.

In embodiments of the present invention, when in organoboron compound (I) containing only there are one the organic boronic primitives In it is a kind of when, the polymer chain can be selected from it is following any or appoint it is several：Molecular weight is no more than the small molecule of 1000Da Alkyl, molecular weight are more than the polymer chain residue of 1000Da.Suitable organoboron compound (I) structure example formed is as follows：

Wherein, g, h, j are each independently a fixed value or average value, g >=20, h >=20, j >=6.

The structure of the organoboron compound (I) of the example above is only that organoboron compound (I) is better described in this condition Typical structure possessed by lower and propose, only thus under the conditions of some more representational structures, rather than the present invention is protected The restriction of range.

In embodiments of the present invention, when in organoboron compound (I) containing organic described in two or more Any one of boric acid primitive or appoint it is several when, the connection structure L₂It can be selected from following any or appoint several：It is singly-bound, miscellaneous Atom linker, molecular weight no more than 1000Da divalent or multivalence small molecule alkyl, molecular weight more than 1000Da divalent or Multivalence polymer chain residue.

Work as L₃、L₄When selected from singly-bound, boron boron singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon list can be selected from Key, boron nitrogen singly-bound；L₃、L₄Preferably boron boron singly-bound, boron carbon single bond, carbon-carbon single bond.The suitable organoboron compound (I) formed Structure example is as follows：

Wherein, h is a fixed value or average value, h >=20.

Work as L₃、L₄When selected from hetero atom linker, it can be selected from following any or appoint several combinations：Ether, sulfenyl, Thioether group, divalent tertiary amine groups, trivalent tertiary amine groups, divalent silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalent phosphorus base, three valent phosphors base, two Valence boryl, trivalent boryl；L₃、L₄Preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups.The suitable organic boron formed Compound (I) structure example is as follows：

Work as L₃、L₄When being no more than the divalent or multivalence small molecule alkyl of 1000Da selected from molecular weight, 1 to 71 are typically contained The valence state of a carbon atom, alkyl can be 2-144 valences, can contain heteroatom group, can be free of has heteroatom group.Briefly Say, the divalent or multivalence 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 or any by hydridization form：Two to one hundred four ten tetravalence C_1-71Alkyl, two to one hundred four ten tetravalence ring C_3-71 Alkyl, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred four ten tetravalence aryl；L₃、L₄It is preferred that two arrive tetravalence methyl, two Octavalence propyl is arrived to sexavalence ethyl, two, two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valence cyclopenta, two to ten Cyclohexyl radicals, two arrive sexavalence phenyl.Suitable organoboron compound (I) structure example formed is as follows：

Work as L₃、L₄Can be any appropriate when being more than the divalent or multivalence polymer chain residue of 1000Da selected from molecular weight Divalent or multivalence polymer chain residue include but are not limited to divalent or multivalence carbochain polymer residue, divalent or multivalence heterochain Polymer residue, divalent or element of multivalence organic polymer residue；Wherein, polymer can be homopolymer, or appoint several lists The copolymer of body, oligomer or polymer composition, polymer chain can be flexible chain or rigid chain.

Work as L₃、L₄Can be that any appropriate macromolecular main chain is main when selected from divalent or multivalence carbochain polymer residue The polymer residue being made of carbon atom, can be selected from by it is any in the following group, any it is unsaturated in the form of, any quilt Substitution form is any by hydridization form：Divalent or multivalence polyolefins chain residue, as divalent or multivalence Polyethylene Chain are residual Base, 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 alcohol chain Residue, divalent or multivalence Polyvinylalkylethers chain residue, divalent or multivalence polybutadiene chain residue, divalent or the poly- isoamyl of multivalence Diene chain residue, divalent or multivalence polychlorobutadiene chain residue, divalent or multivalence polynorbornene chain residue etc.；Divalent or multivalence Polyacrylic chain residue, as divalent or multivalence polyacrylic acid chain residue, divalent or multivalence polyacrylamide chain residue, divalent or Multivalence polymethyl acrylate chain residue, divalent or multivalence polymethyl methacrylate chain residue etc.；Divalent or multivalence polyacrylonitrile Class chain residue, such as divalent or multivalence polyacrylonitrile chain residue.L₃、L₄It is preferred that divalent or multivalence Polyethylene Chain residue, divalent or more Valence polypropylene chains residue, divalent or multivalence polystyrene chain residue, divalent or multivalence polyvinyl chloride chain residue, divalent or multivalence are poly- Butadiene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polyacrylic acid chain residue, divalent or multivalence are poly- Acrylamide chain residue, divalent or multivalence polyacrylonitrile chain residue.Suitable organoboron compound (I) structure example formed is such as Under：

Wherein, g, h, i, j, k are each independently a fixed value or average value, preferably g >=20, h >=20, i >=20, j ≥6、k≥6。

Work as L₃、L₄Can be that any appropriate macromolecular main chain is main when selected from divalent or multivalence heterochain polymer residue The polymer residue being made of the hetero atoms such as carbon atom and nitrogen, oxygen, sulphur, can be selected from it is any in the following group, any not Saturated 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, Divalent 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.；Two Valence or multivalence polyesters chain residue, such as divalent or multivalence polycaprolactone chain residue, divalent or the poly- valerolactone chain residue of multivalence, divalent Or multivalence polylactide chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence unsaturation are poly- Ester 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.. L₃、L₄It 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 Chain residue, divalent or multivalence polyurethane chain residue.Suitable organoboron compound (I) structure example formed is as follows：

Work as L₃、L₄Can be any appropriate macromolecular main chain when selected from divalent or element of multivalence organic polymer residue The polymer residue being mainly 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 By it is any in the following group, any it is unsaturated in the form of, 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 poly organo Alkane chain residue, divalent or multivalence poly-organosilicon borine chain residue, divalent or multivalence poly-organosilicon azane chain residue, divalent or multivalence Poly-organosilicon sulfane chain residue, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or the poly- organic metal siloxanes of multivalence Chain residue；Divalent or multivalence organic boron Type of Collective object chain residue, such as the divalent or poly- organo-borane chain residue of multivalence, divalent or multivalence Poly- organic boroxane chain residue, divalent or the poly- organic boron azane chain residue of multivalence, 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 are organic Lead Type of Collective object chain residue；Divalent or multivalence organic tin polymer chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain are residual Base；Divalent or multivalence antimony organic Type of Collective object chain residue.L₃、L₄It is preferred that divalent or multivalence poly-organosilicon alkane chain residue, divalent or more Valence polysiloxane chain residue, divalent or the poly- organo-borane chain residue of multivalence.Suitable organoboron compound (I) knot formed Structure is exemplified below：

In embodiments of the present invention, the organic boronic ester group can be selected from but be not limited only to following any Or appoint several structures：

Wherein, K₂For the group being connected directly with boron atom, it is selected from following any structure：Hydrogen atom, heteroatom group The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；R₁、R₂、R₃、R₄、R₆ For the monovalent organic group or monovalence organosilicon radical being connected directly with oxygen atom, pass through carbon atom or silicon atom and oxygen atom It is connected directly, is selected from following any structure：Small molecule alkyl, molecular weight of the molecular weight no more than 1000Da are no more than Small molecule silylation, the molecular weight of 1000Da are more than the polymer chain residue of 1000Da；R₅To be connected directly with two oxygen atoms Bivalent organic group or divalent organosilicon radical, be connected directly with oxygen atom by carbon atom or silicon atom, selected from Under any structure：Divalent small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are no more than small point of the divalent of 1000Da Sub- silylation, molecular weight are more than the diatomic polymer chain residue of 1000Da；Wherein, the cyclic structure in B9 is containing at least one The nonaro-maticity or armaticity boron heterocyclic group, boron atom of organic boronic ester group are placed in cyclic structure, and cyclic structure can be Small molecule ring can also be macromolecular ring, be preferably 3~100 membered rings, more preferably 3~50 membered rings, more preferably 3~10 Membered ring；The ring member nitrogen atoms of cyclic structure in B9 are each independently carbon atom, boron atom or other hetero atoms, and at least one Ring member nitrogen atoms are boron atom and constitute organic boronic ester group, and at least one ring member nitrogen atoms and compound other atoms are connected；B9 In each ring member nitrogen atoms of cyclic structure on hydrogen atom can be substituted, can not also be substituted；Cyclic structure in B9 can Think single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Indicate with compound its The connection of his atom；Boron atom in the various structures is at least connected with a carbon atom by boron carbon key, and at least one A organic group is keyed to by the boron carbon in boron atom.

Wherein, the cyclic structure in B9 can be selected from by it is any in the following group, any it is unsaturated in the form of, any quilt Substitution form is any by hydridization form：The miscellaneous luxuriant and rich with fragrance, boron of boron heterocycle alkane, boron heterocyclic hydrocarbon, the miscellaneous benzene of boron, the miscellaneous naphthalene of boron, the miscellaneous anthracene of boron, boron Heteroaryl hydrocarbon；The preferred boron heterocycle pentane of listed cyclic structure, boron azacyclohexane, boron heterocycle hexene, boron heterocycle hexadiene, boron heterocycle The miscellaneous benzene of hexenone, boron.Citing is such as：

In embodiments of the present invention, there are in the organic boron compound of organic boronate and/or organic boronic ester group, one A hydroxyl and an ester group can be connected in boron atom simultaneously, can also contain at least one boric acid simultaneously in the same module Base and at least one boric acid ester group, citing is such as：

Compound contains organic boron acidic group and organic boronic ester group simultaneously helps to regulate and control its dissolubility, reaction rate, anti- The parameters such as degree are answered, and the performances such as dynamic that can be used for regulating and controlling dynamic aggregation object.

In embodiments of the present invention, when in the organoboron compound (I) contain two or more structures When primitive, connection structure L can be passed through₃、L₄It interconnects, can also be connected in cyclic annular or cluster side group/side chain；When Only there are one when the structural motif, can be connected to not cyclic or not at any position of the polymer chain of cluster.

In embodiments of the present invention, when in organoboron compound (I) containing organic described in two or more Any one of boric acid primitive or appoint it is several when, the connection structure L₃、L₄It can be selected from following any or appoint several：Singly-bound, The divalent of hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the divalent of 1000Da Or multivalence polymer chain residue；The connection structure L₂Selecting party of the specific choice with reference to connection structure in B1, B2, B3, B4 Formula, which is not described herein again, can be exemplified below：

Wherein, g, h, j are each independently a fixed value or average value, preferably g >=20, h >=20, j >=6.

In embodiments of the present invention, the organic boronic alkali can be selected from but be not limited only to following any Or appoint several structures：

Wherein, K₃For the group being connected directly with boron atom, it is selected from following any structure：Hydrogen atom, heteroatom group Group, fatty oxyl, fragrant oxyl, small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are poly- more than 1000Da Close object chain residue；M is any appropriate metallic element or any appropriate ionic group in the periodic table of elements, and n is the valence mumber of M, It is preferred that+1 valence ,+divalent ,+trivalent, citing such as lithium ion, potassium ion, sodium ion, magnesium ion, calcium ion, iron ion, copper ion and ammonium Radical ion etc.；Wherein, the cyclic structure in B13 is that the nonaro-maticity containing at least one organic boronic ester group or armaticity boron are miscellaneous Cyclic group, boron atom are placed in cyclic structure；It is former that the ring member nitrogen atoms of cyclic structure in B13 are each independently carbon atom, boron Son or other hetero atoms, and at least one ring member nitrogen atoms are boron atom and constitute organic boronic ester group, and at least one cyclization is former Other atoms are connected son with compound；Boron atom in the various structures is at least connected with a carbon atom by boron carbon key, And at least one organic group is keyed to by the boron carbon in boron atom；

In embodiments of the present invention, when in organoboron compound (I) containing organic described in two or more Any one of boric acid primitive or appoint it is several when, the connection structure L₃、L₄It can be selected from following any or appoint several：Singly-bound, The divalent of hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the divalent of 1000Da Or multivalence polymer chain residue；The connection structure L₃、L₄Selection of the specific choice with reference to connection structure in B1, B2, B3, B4 Mode, which is not described herein again, can be exemplified below：

Wherein, j is a fixed value or average value, preferably j >=20.

In embodiments of the present invention, the organic boron alkylhalide group can be selected from but be not limited only to following any Or appoint several structures：

Wherein, K₄For the group being connected directly with boron atom, it is selected from following any structure：Hydrogen atom, heteroatom group Group, fatty oxyl, fragrant oxyl, small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are poly- more than 1000Da Close object chain residue；G₁~G₅It is each independently selected from fluorine atom, chlorine atom, bromine atom, iodine atom；Wherein, the cyclic annular knot in B17 Structure is that the nonaro-maticity containing at least one organic boronic ester group or armaticity boron heterocyclic group, boron atom are placed in cyclic structure In；The ring member nitrogen atoms of cyclic structure in B17 are each independently carbon atom, boron atom or other hetero atoms, and at least one Ring member nitrogen atoms are boron atom and constitute organic boronic ester group, and at least one ring member nitrogen atoms and compound other atoms are connected；Institute It states the boron atom in various structures to be at least connected by boron carbon key with a carbon atom, and at least one organic group passes through institute Boron carbon is stated to be keyed in boron atom；

In embodiments of the present invention, when in organoboron compound (I) containing organic described in two or more Any one of boric acid primitive or appoint it is several when, the connection structure L₃、L₄It can be selected from following any or appoint several：Singly-bound, The divalent of hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the divalent of 1000Da Or multivalence polymer chain residue；The connection structure L₃、L₄Selection of the specific choice with reference to connection structure in B1, B2, B3, B4 Mode, which is not described herein again, and suitable organoboron compound (I) structure example of formation is as follows：

In embodiments of the present invention, in a kind of organoboron compound (I), can contain simultaneously organic boron acidic group, Any one of organic boronic ester group, organic boronic alkali and organic boron alkylhalide group appoint several structures, remove above-mentioned some examples Outside, it can also be exemplified below：

In embodiments of the present invention, the compound (II) of the primitive containing dihydroxy, can be selected from but not only limit In following any or several structures：

Wherein,The connection of other atoms of expression with compound；R₇~R₉For the univalent perssad being connected with dihydroxy primitive, It is each independently selected from the small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, contains heteroatom group Molecular weight be more than the macromolecule polyalcohol chain residue of 1000Da no more than the small molecule alkyl of 1000Da, molecular weight；

Wherein, L be dihydroxy primitive in connection hydroxyl two carbon atoms between linker, may include carbon atom and Oxygen, nitrogen, sulfur heteroatom connect the nearest skeletal atom number no more than 3 of two hydroxyls and do not form a diphenol；

Wherein, the heteroatom group can be selected from following any group：Halogen, hydroxyl, mercaptan, ether, thioether Base, carboxyl, nitro, primary amine groups, secondary amine, silicon substrate, phosphorus base, triazole, isoxazole, ethylene ehter bond, amide groups, imide, Thioamides base, enamine base, carbonate group, carbamate groups, thiocarbamate base, thioester substrate, ortho acid ester group, phosphoric acid It is ester group, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio Phosphorous acyl group, thio secondary phosphoryl, phosphorus silane ester group, silane ester group, carbamide, thioamides, phosphamide, phosphoramidite, coke Phosphamide, cyclophosphamide, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, diazanyl, hydrazide group, thio carbohydrazide base, Azo carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, thiocarbazates base, carbonohydrazides, thio kappa Hydrazine, azo group, isourea base, isothiourea group, allophanate group, thioallophanate base, guanidine radicals, amidino groups, amino guanidine radicals, amino Amidino groups, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonate group, sulfinat, sulfonamide Base, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide；It is preferred that primary amine groups, amide groups；

Wherein, work as R₇~R₉It is each independently selected from small molecule alkyl of the molecular weight no more than 1000Da, contains heteroatom group When the molecular weight of group is no more than the small molecule alkyl of 1000Da, contain 1 to 71 carbon atoms, type is not particularly limited, and wraps Contain but is not limited only to C_1-71Alkyl, substituted C_1-71Alkyl, undersaturated C_1-71The C of alkyl, hydridization_1-71Alkyl, substituted open chain Miscellaneous C_1-71Alkyl, ring C_3-71Alkyl, substituted ring C_3-71Alkyl, undersaturated ring C_3-71The ring C of alkyl, hydridization_3-71Alkyl, benzene Base, benzyl, substituted phenyl, substituted benzyl, aryl, substituted aryl, heteroaryl alkyl, substituted heteroaryl alkyl；R₇ ~R₉Preferably methyl, ethyl, propyl, propylene, butyl, butylene, amyl, hexyl, heptyl, octyl, nonyl, decyl；R₇~R₉More Preferably methyl, ethyl, propyl；

Wherein, work as R₇~R₉It, can when being each independently selected from macromolecule polyalcohol chain residue of the molecular weight more than 1000Da For any appropriate polymer chain residue, it is organic to include but are not limited to carbochain polymer residue, heterochain polymer residue, element Polymer residue, wherein polymer can be homopolymer, copolymer；

Wherein, work as R₇~R₉When being each independently selected from carbochain polymer residue, can be selected from it is any in the following group, appoint A kind of unsaturated form, any substituted form or any by hydridization form：Polyethylene Chain residue, polypropylene chains Residue, polyisobutene chain residue, polystyrene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain Residue, polytetrafluoroethylene (PTFE) chain residue, polytrifluorochloroethylene chain residue, polyacrylic acid chain residue, polyacrylamide chain residue, poly- third E pioic acid methyl ester chain residue, polymethyl methacrylate chain residue, polyacrylonitrile chain residue, polyvinyl alcohol chain residue, polyvinyl Alkyl ether chain residue, polybutadiene chain residue, polyisoprene chain residue, polychlorobutadiene chain residue；R₇~R₉It is preferred that polyethylene Chain residue, polypropylene chains residue, polyvinyl chloride chain residue, polyacrylic acid chain residue, polyacrylamide chain residue, polymethyl Sour methyl esters chain residue, polyvinyl alcohol chain residue；

Wherein, work as R₇~R₉When being each independently selected from heterochain polymer residue, can be selected from it is any in the following group, appoint A kind of unsaturated form, any substituted form or any by hydridization form：Polyether chain residue, polyester chain are residual Base, polyethylene oxide chain residue, poly bis (chloromethyl) fourth oxygen loop chain residue, polyphenylene oxide chain residue, asphalt mixtures modified by epoxy resin fat chain residue, poly- pair Ethylene terephthalate chain residue, polycarbonate chain residue, unsaturated-resin chain residue, alkyd resin chain residue, polyamide Chain residue, polysulfones chain residue, phenolic resin chain residue, Lauxite chain residue；R₇~R₉Preferred, polyethers chain residue, polyester chain are residual Base, polyethylene oxide chain residue, asphalt mixtures modified by epoxy resin fat chain residue, polyethylene terephthalate chain residue, polycarbonate chain residue, Unsaturated-resin chain residue, polyamide chains residue；

Wherein, work as R₇~R₉When being each independently selected from elemento-organic polymer residue, it can be selected from any in the following group Kind, any unsaturated form, any substituted form or any by hydridization form：Polysiloxane chain is residual Base, organic silica carbon polymer chain residue, poly- alkyl silica amine chain residue, poly- alkyl silithiane chain residue, poly- organic metal silicon Oxygen alkane chain residue, boracic organic polymer chain residue, polytitanoorganosiloxane chain residue, gathers poly- organo-aluminium siloxane chain residue Organotin siloxane chain residue, leaded polymer chain residue, poly- antimony organic siloxane chain residue, poly- organophosphor siloxane chain are residual Base, organo-fluorine polymer chain residue, organophosphorus polymer chain residue, organo-boron polymer chain residue；R₇~R₉It is preferred that poly-organosilicon Oxygen alkane chain residue；

Wherein, work as R₇~R₉It is each independently selected from small molecule alkyl of the molecular weight no more than 1000Da, contains heteroatom group When small molecule alkyl of the molecular weight of group no more than 1000Da, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da, Structure is not particularly limited, can be straight chain type, branched chain type, multi-arm structural type, star-like, H-type, combed, dendritic, mononuclear type, Polycyclic type, loop coil type, condensed ring type, bridged ring type, nesting chain ring-like, with cyclic structure, two and three dimensions cluster type；

Wherein, as L when singly-bound in linear structure, the singly-bound refer to two carbon atoms being connected with hydroxyl it Between the carbon-carbon single bond that is formed, dihydroxy primitive is 1,2- glycol primitives at this time；

Wherein, as L when methylene in linear structure, dihydroxy primitive is 1,3- glycol primitives, methylene at this time On hydrogen atom can be replaced by arbitrary substituent group, can not also be substituted, the substituent group is each independently hetero atom The small molecule alkyl of group, molecular weight no more than 1000Da, the molecular weight containing heteroatom group are no more than small point of 1000Da Sub- alkyl, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da, are specifically defined and can refer to R₇~R₉, no longer superfluous here It states；

Wherein, the isomeric form of D1~D4 is each independently selected from any in position isomery, conformational isomerism, chiral photo-isomerisation Kind；

Wherein, the position isomery include due to substituent group, functional group or linking group on dihydroxy primitive position Difference and the position heterogeneous structure that generates.For example, working as R₇~R₈When selected from same substituent group, the position heterogeneous structure of D2 can be：

Similarly, D1~D4 also has its position heterogeneous structure；

Wherein, the conformational isomerism includes and rotates to cause atom due to various different arrange in space around key because of intramolecular The conformational isomerism structure of generation；

Wherein, the chiral photo-isomerisation includes the chiral photo-isomerisation structure for being mirror each other.It is selected from carbon-carbon single bond with L Example, when two carbon atoms of 1,2- glycol primitives are asymmetric carbon atom, the alloisomerism structure of D1 can be：

Similarly, D2~D4 also has its chiral photo-isomerisation structure.

Above-mentioned heterogeneous structure is only preferably said possessed typical structure under the conditions of this and is proposed, rather than is protected to the present invention Protect the restriction of range.

Wherein, when L is selected from aliphatic ring, at least one participations of two carbon atoms being connected directly with two hydroxyls at Ring, when two carbon atoms are involved in cyclization, the dihydroxy primitive of formation is 1,2- glycol primitives, when only there are one carbon atoms to join When with cyclization, the dihydroxy primitive of formation is 1,3- glycol primitives；Cyclic structure be 3~200 membered rings, preferably 3~50 membered rings, more It is preferred that 3~10 membered rings, the quantity of cyclic structure is 1,2 or more；It can be any alicyclic ring or alicyclic heterocyclic, and cyclic Atom is each independently carbon atom or hetero atom；The hetero atom can be selected from nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, Silicon atom, boron atom；Hydrogen atom on aliphatic ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted； The substituent group is each independently the small molecule alkyl of heteroatom group, molecular weight no more than 1000Da, contains hetero atom Small molecule alkyl of the molecular weight of group no more than 1000Da, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da, It is specifically defined and can refer to R₁~R₃, which is not described herein again.It says to overview, the alicyclic ring and alicyclic heterocyclic include but not limited to ring C_3-200 Alkane, ethylene oxide, azietine, side's acid, cyclobutanedinone, semi-square acid, cyclopentadienyl, tetrahydrofuran, pyrrolidines, thiazolidine, dihydro Isoxazole, oxazolidines, cyclohexene, oxinane, piperidines, 1,4- dioxane, norbornane, norbornene, norbornadiene, 1,4,7- 7-triazacyclononanes, cycleanine, furans, thiophene, pyrroles, imidazoles, oxazole, isoxazoles, thiazole, isothiazole, pyrazoles, Caprolactone etc.；The alicyclic ring and the preferred cyclopropane of alicyclic heterocyclic, cyclobutane, pentamethylene, hexamethylene, cycloheptane, cyclooctane, ring nonyl Alkane, cyclodecane, ethylene oxide, furans, thiophene, pyrroles；The alicyclic ring and the more preferable cyclopropane of alicyclic heterocyclic, cyclobutane, pentamethylene, Hexamethylene.Citing is such as：

Wherein, when L is selected from aromatic ring, at least one participations of two carbon atoms being connected directly with two hydroxyls at Ring, when two carbon atoms are involved in cyclization, the dihydroxy primitive of formation is adjacent two phenolic hydroxyl group primitives, when only there are one carbon atoms When participating in cyclization, the dihydroxy primitive of formation is 2- hydroxymethyl phenol hydroxyl primitives；Cyclic structure be 3~200 membered rings, preferably 3~ The quantity of 50 membered rings, more preferable 3~10 membered ring, cyclic structure is 1,2 or more；It can be that any aromatic ring or virtue are miscellaneous Ring, and ring member nitrogen atoms are each independently carbon atom or hetero atom；When two hydroxyls are all directly coupled on aromatic ring, two The position relationship of hydroxyl is ortho position；The hetero atom can be selected from nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron Atom；Hydrogen atom on aromatic ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；The substitution Base is each independently heteroatom group, molecular weight is no more than small molecule alkyl, the molecule containing heteroatom group of 1000Da Small molecule alkyl of the amount no more than 1000Da, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da, and being specifically defined can With reference to R₁~R₃, it is described which is not described herein again.

The aromatic ring, is a kind of polyenic compounds with coplanar annular closed conjugated system, and the chemical combination The pi-electron number of object meets general formula 4n+2 (n is natural number).

The pi-electron be exactly with P orbital electron participate in bonding electronics, wherein P tracks are a kind of atomic orbitals, Angular-momentum quantum number is 1, and magnetic quantum number can be -1,0 or+1, and in each P shells in there are three P tracks, Px, Py, Pz, shapes All identical but direction is different, each to accommodate 2 electronics, and therefore, P tracks can at most accommodate 6 electronics.In general, every One double bond has 2 pi-electrons, each three key has 4 pi-electrons.

It says to overview, the aromatic ring or heteroaromatic include but not limited to phenyl ring, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5- Triazine, indenes, dihydroindene, indoles, iso-indoles, purine, naphthalene, anthracene, dihydroanthracene, xanthene (xanthene), thio xanthene, phenanthrene, dihydro Phenanthrene, 10,11- dihydro -5H- dibenzo [a, d] cycloheptane, dibenzocycloheptene, 5- dibenzosuberenones, quinoline, isoquinolin, Fluorenes, carbazole, iminodibenzyl, naphthalene second ring, dibenzo cyclooctyne, azepine dibenzo cyclooctyne etc.；The aromatic ring or heteroaromatic are excellent Select phenyl ring, pyridine.Citing is such as：

When cyclic structure is selected from aliphatic ring, aromatic ring, the cyclic structure simultaneously containing aliphatic ring and aromatic ring When, structure is not particularly limited.It can be single ring architecture, i.e., containing only there are one rings in structure, citing is such as：

It can be multiring structure, i.e., contain two or more independent rings in structure, citing is such as：

It can be spirane structure, i.e., contain in structure and pass through a shared atomic building to each other by two or more rings Cyclic structure, citing is such as：

Can be condensed cyclic structure (wherein also including two rings, virtue and ring structure), i.e., containing by two or more rings in structure To each other by sharing the cyclic structure of two adjacent atomic buildings, citing is such as：

Can be caged scaffold, i.e., containing more than two adjacent by sharing to each other by two or more rings in structure The cyclic structure of atomic building, citing is such as：

It can be nested rings structure, i.e., contain the ring-type being connected to each other by two or more rings or nesting is constituted in structure Structure, citing is such as：

Or with the combination for several cyclic structures of taking up an official post.

Two are lifted below as possessed structure when being selected from cyclic structure containing dihydroxy primitive to cyclic structure Explanation.

For example, when cyclic structure is selected from cyclopropane, it is selected from following any structure or its isomeric form：

Wherein, it is different to be each independently selected from position isomery, conformational isomerism, cis-trans isomerism, chirality for the isomeric form of E1~E4 It is any in structure.

Wherein, the position heterogeneous structure includes since substituent group, functional group or linking group are in 1,2- glycol primitives The difference of position in the cyclic structure at place and the position heterogeneous structure generated.For example, the position heterogeneous structure of E1 can be

Similarly, E2~E4 also has its position heterogeneous structure；

Wherein, the cis-trans isomerism structure include due to the presence of ring limit σ keys rotate freely and generate along anti- Heterogeneous structure.For example, the cis-trans isomerism structure of E1 can be

Similarly, E2~E4 also has its cis-trans isomerism structure；

Wherein, the conformational isomerism structure include caused by intramolecular rotate around key atom different arranged in the various of space The conformational isomerism structure for arranging and generating.For example, the conformational isomerism structure of E1 can be

Similarly, E2~E4 also has its conformational isomerism structure；

Wherein, the chiral photo-isomerisation structure includes the chiral photo-isomerisation structure for being mirror each other.For example, the solid of E1 Heterogeneous structure can be

Similarly, E2~E4 also has its chiral photo-isomerisation structure；

For another example when cyclic structure is selected from phenyl ring, it is selected from following any structure or its position heterogeneous structure：

Wherein, the position heterogeneous structure includes since substituent group, functional group or linking group are in 1,3- glycol primitives The difference of position on the ring member nitrogen atoms of the cyclic structure at place and on the carbon atom of 1,3- glycol primitives and the position isomery that generates Structure.For example, the position heterogeneous structure of F1 can be

Similarly, F2~F6 also has its position heterogeneous structure；

It can be interconnected by following any or several linker T between two or more dihydroxy primitives Come from different backgrounds and possess different abilities alcoholic compound, and linker T can be selected from：Singly-bound or unsaturated bond, hetero atom linker, molecular weight are no more than 1000Da Divalent or multivalence small molecule alkyl, molecular weight containing heteroatom group be no more than the divalent or multivalence small molecule hydrocarbon of 1000Da The divalent of base, molecular weight more than 1000Da or multivalence polymer chain residue, molecular weight are more than the divalent or polyvalent mineral of 1000Da Macromolecular.At this point, compound (II) structure example of the suitable primitive containing dihydroxy formed is as follows：

Wherein, g is a fixed value or average value, g >=36.

The compound (II) of the primitive containing dihydroxy of the example above is only that the compound of the primitive containing dihydroxy is better described (II) with this condition possessed by structure and propose, the typical structure of proposition only thus under the conditions of some most representative knots Structure rather than limiting the scope of the present invention.

When T is selected from singly-bound or unsaturated bond, it is selected from following any structure：Carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen list Key, carbon-carbon double bond, aromatic radical；It is preferred that carbon-carbon single bond.Compound (II) structure example of the suitable primitive containing dihydroxy formed It is as follows：

When T is selected from hetero atom linker, it can be selected from following any or appoint several combinations：Ether, thioether group, secondary amine Base, tertiary amine groups, silicon substrate, phosphorus base, triazole, isoxazole, triazine, ethylene ehter bond, amide groups, imide, thioamides base, alkene Amido, carbonate group, carbamate groups, thiocarbamate base, thioester substrate, ortho acid ester group, phosphate-based, phosphite ester It is base, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio Secondary phosphoryl, phosphorus silane ester group, silane ester group, carbamide, thioamides, phosphamide, phosphoramidite, pyrophosphoramide, ring phosphinylidyne Amine, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, thioamides key, diazanyl, hydrazide group, thio carbohydrazide base, idol Nitrogen carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, thiocarbazates base, carbonohydrazides, thiocarbohydrazide, Azo group, isourea base, isothiourea group, allophanate group, thioallophanate base, guanidine radicals, amidino groups, amino guanidine radicals, amino amidine Base, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonate group, sulfinat, sulfoamido, Sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide；Hetero atom linker be preferably ether, thioether group, secondary amine, Tertiary amine groups, amide groups, carbonate group, carbamate groups, urea groups.The compound (II) of the suitable primitive containing dihydroxy formed Structure example is as follows：

When T is selected from divalent of the molecular weight no more than 1000Da or multivalence small molecule alkyl or contains the molecule of heteroatom group When amount is no more than the divalent or multivalence small molecule alkyl of 1000Da, there are 1 to 71 carbon atoms, and the valence state of alkyl is 2- 144 valences, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form or any quilt Hydridization form：Two to one hundred four ten tetravalence C_1-71Alkyl, two to one hundred four ten tetravalence ring C_3-71Alkyl, two arrive to sexavalence phenyl, two Octavalence benzyl, two to one hundred four ten tetravalence aryl；T preferably two arrives octavalence propyl to tetravalence methyl, two to sexavalence ethyl, two, Two arrive sexavalence phenyl to sexavalence cyclopropane base, two to octavalence cyclobutyl, two to ten valence cyclopenta, two to ten cyclohexyl radicals, two. Compound (II) structure example of the suitable primitive containing dihydroxy formed is as follows：

When T, which is selected from the molecular weight containing heteroatom group, is no more than the small molecule alkyl of 1000Da, in small molecule alkyl Following any or several heteroatom groups can be contained：Halogen, hydroxyl, mercaptan, ether, thioether group, carboxyl, nitro, primary amine Base, secondary amine, silicon substrate, phosphorus base, triazole, isoxazole, ethylene ehter bond, amide groups, imide, thioamides base, enamine base, It is carbonate group, carbamate groups, thiocarbamate base, thioester substrate, ortho acid ester group, phosphate-based, phosphorous acid ester group, secondary Phosphate-based, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphinylidyne Base, phosphorus silane ester group, silane ester group, carbamide, thioamides, phosphamide, phosphoramidite, pyrophosphoramide, cyclophosphamide, different ring Phosphamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, thioamides key, diazanyl, hydrazide group, thio carbohydrazide base, azo carbonyl acyl Diazanyl, thio azo carbonyl hydrazide group, carbazic acid ester group, thiocarbazates base, carbonohydrazides, thiocarbohydrazide, azo group, 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, sulfinat, sulfoamido, sulfenyl Amido, sulfonyl hydrazino, sulfonylurea group, maleimide.

Can be any appropriate two when T, 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, copolymer；

When T is selected from divalent or multivalence carbochain polymer residue, 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 Polyethylene Chain residue, divalent or more Valence polypropylene chains residue, divalent or multivalence polyisobutene chain residue, divalent or multivalence polystyrene chain residue, divalent or multivalence are poly- Vinyl chloride chain residue, divalent or multivalence Vingon chain residue, divalent or multivalence polyvinyl fluoride chain residue, divalent or multivalence are poly- Tetrafluoroethene chain residue, divalent or multivalence polytrifluorochloroethylene chain residue, 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, divalent or multivalence polyacrylonitrile chain residue, divalent or multivalence polyvinyl alcohol chain residue, divalent or multivalence polyvinyl alkyl Ether chain residue, divalent or multivalence polybutadiene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polychlorostyrene fourth Diene chain residue；The preferred divalent of T or multivalence Polyethylene Chain residue, divalent or multivalence polypropylene chains residue, divalent or multivalence polychlorostyrene Ethylene chain residue, divalent or multivalence polyacrylamide chain residue, divalent or multivalence polymethyl acrylate chain residue, divalent or multivalence Polymethyl methacrylate chain residue.Compound (II) structure example of the suitable primitive containing dihydroxy formed is as follows：

Wherein, g, h respectively stand alone as a fixed value or average value, g >=36, h >=10.

When T is selected from divalent or multivalence heterochain polymer residue, 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 polyether chain residue, divalent or multivalence Polyester chain residue, divalent or multivalence polyethylene oxide chain residue, divalent or poly bis (chloromethyl) the fourth oxygen loop chain residue of multivalence, divalent Or multivalence polyphenylene oxide chain residue, divalent or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalent or multivalence polyester resin chain residue, divalent or more Valence polycarbonate chain residue, divalent or multivalence unsaturated-resin chain residue, divalent or multivalence alkyd resin chain residue, divalent or more Valence polyamide chains residue, divalent or multivalence phenolic resin chain residue, divalent or multivalence Lauxite chain residue；The preferred divalent of T or Multivalence polyether chain residue, divalent or multivalence polyester chain residue, divalent or multivalence polyethylene oxide chain residue, divalent or multivalence epoxy Resin chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence polycarbonate chain residue, divalent Or multivalence unsaturated-resin chain residue, divalent or multivalence polyamide chains residue.The chemical combination of the suitable primitive containing dihydroxy formed Object (II) structure example is as follows：

Wherein, h is a fixed value or average value, h >=10.

When T is selected from divalent or element of multivalence organic polymer residue, can be selected from any in the following group, any Unsaturated form, any substituted form or any by hydridization form：Divalent or multivalence polysiloxane chain are residual Base, divalent or the organic silica carbon polymer chain residue of multivalence, divalent or the poly- alkyl silica amine chain residue of multivalence, divalent or multivalence are poly- Alkyl silithiane chain residue, divalent or the poly- organic metal siloxane chain residue of multivalence, divalent or the poly- organo-aluminium siloxane chain of multivalence Residue, divalent or multivalence boracic organic polymer chain residue, divalent or multivalence polytitanoorganosiloxane chain residue, divalent or multivalence Polyorganostannosiloxanes chain residue, divalent or the leaded polymer chain residue of multivalence, divalent or the poly- antimony organic siloxane chain of multivalence are residual Base, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or multivalence organo-fluorine polymer chain residue, divalent or multivalence are organic Phosphorus polymer chain residue, divalent or multivalence organo-boron polymer chain residue；The preferred divalent of T or multivalence polysiloxane chain are residual Base.Compound (II) structure example of the suitable primitive containing dihydroxy formed is as follows：

Wherein, g is a fixed value or average value, g >=15.

When T, which is selected from molecular weight, is more than the divalent or polyvalent mineral macromolecular of 1000Da, can be selected from any in the following group Kind or any surface modified product：Polysilane, zeolite-type molecular sieves, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropoly acid Molecules of salt sieve, diamond, graphite, graphene, graphene oxide, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five oxygen Change phosphorus, polyphosphoric acid, polyphosphazene, polychlorostyrene for phosphonitrile, molybdenum sulfide, silica, silicon disulfide, silicon nitride, silicon carbide, talcum, height Ridge soil, montmorillonite, mica, asbestos, cement, glass, glass fibre, ceramics, boron oxide, nitridation sulphur, calcium silicide, beryllium oxide, oxygen It is poly- to change magnesium, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, diaspore, gibbsite, corundum, titanium dioxide, phthalocyanine Close object；Graphene that T is modified preferably through surface, the carbon fiber being modified by surface, silica, the warp being modified by surface Cross the glass fibre of surface modification.

When T is selected from divalent of the molecular weight no more than 1000Da or multivalence small molecule alkyl, contains the molecule of heteroatom group Divalent of the amount no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the divalent or multivalence polymer chain residue of 1000Da When, structure is not particularly limited, and can be straight chain type, branched chain type, multi-arm structural type, star-like, H-type, combed, dendritic, list Ring-like, polycyclic type, loop coil type, condensed ring type, bridged ring type, nesting chain ring-like, with cyclic structure, two and three dimensions reticular pattern.

In special circumstances, by sharing a carbon atom, sharing a carbon carbon list between two or more dihydroxy primitives Key or the form for sharing a carbon-carbon double bond come from different backgrounds and possess different abilities alcoholic compound, the compound of the suitable primitive containing dihydroxy of formation (II) structure example is as follows：

In embodiments of the present invention, the compound (III) containing single hydrocarbon hydroxyl primitive comprising but not only limit In containing single alkanol primitive, monoene alcohol primitive, single phenol hydroxyl primitive compound and containing in meta position polyphenol hydroxyl primitive, place In the polyol of the hydroxyl of at least four atoms of polyphenol hydroxyl primitive and interval of contraposition.When in compound (III) Containing only there are one when single hydrocarbon hydroxyl primitive, it can be selected from but be not limited only to any of lower structure：

Wherein, R₁₀~R₁₁For the univalent perssad being connected with single hydrocarbon hydroxyl primitive, it is each independently selected from hydrogen atom, miscellaneous original Subbase group, molecular weight are small no more than 1000Da's no more than the small molecule alkyl of 1000Da, the molecular weight containing heteroatom group Molecule alkyl, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da；It, which is specifically defined, can refer to dihydroxy primitive structure Middle substituent R₇~R₉Selection mode, details are not described herein；Wherein, the cyclic structure in M4, M5 is to contain at least one hydroxyl Nonaro-maticity or armaticity cyclic group, carbon atom be placed in cyclic structure, cyclic structure can be small molecule ring, can also be Macromolecular ring is preferably 3~100 membered rings, more preferably 3~50 membered rings, more preferably 3~10 membered rings；Ring-type in M4, M5 The ring member nitrogen atoms of structure are each independently carbon atom, silicon atom, oxygen atom or other hetero atoms；Cyclic structure in M4, M5 Hydrogen atom on each ring member nitrogen atoms can be substituted, and can not also be substituted；Cyclic structure in M4, M5 can be monocycle knot Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Citing is such as：

Wherein,Indicate the company of polymer chain, crosslinking link or any other suitable group (including hydrogen atom) It connects；

In the present invention, when the described compound containing single hydrocarbon hydroxyl primitive is present in polymer, and there are two or When multiple connections, it can be connected to not cyclic or not at cyclic annular or group in the polymer chain of cluster, can also be connected to In side group/side chain of cluster；When only there are one the connection when, any position of polymer chain can be connected to.The conjunction of formation Suitable compound (III) structure example containing single hydrocarbon hydroxyl primitive is as follows：

Wherein, g, h respectively stand alone as a fixed value or average value, g >=15, h >=10.

The compound (III) containing single hydrocarbon hydroxyl primitive of the example above is only that the change containing single hydrocarbon hydroxyl primitive is better described Close object (III) with this condition possessed by typical structure and propose, only thus under the conditions of some more representational structures, Rather than limiting the scope of the present invention.

In embodiments of the present invention, the compound (III) containing single hydrocarbon hydroxyl primitive, including wherein wrapping It includes but is not limited only to containing single alkanol primitive, monoene alcohol primitive, the compound of single phenol hydroxyl primitive and containing the polyphenol in meta position The polyol of the hydroxyl of at least four atoms of hydroxyl primitive, the polyphenol hydroxyl primitive in contraposition and interval.Working as When closing in object (III) containing two or more single hydrocarbon hydroxyl primitives, company can be passed through between two or more list hydrocarbon hydroxyl primitives Connect base be connected, single hydrocarbon hydroxyl primitive can be any one of M1, M2, M3, M4, M5 or appoint it is several, formed such as M6, M7 or M8 Structure：

Wherein,Indicate polymer chain, crosslinking link or the connection of any other suitable group (including hydrogen atom)；

Wherein, R₁₂~R₁₃For the univalent perssad being connected with single hydrocarbon hydroxyl primitive, it is each independently selected from hydrogen atom, miscellaneous original Subbase group, molecular weight are small no more than 1000Da's no more than the small molecule alkyl of 1000Da, the molecular weight containing heteroatom group Molecule alkyl, molecular weight are more than the macromolecule polyalcohol chain residue of 1000Da；It is specifically defined can refer to and be taken in dihydroxy primitive For base R₇~R₉Selection mode, details are not described herein；

Wherein, L₁、L₂For the linker between two single hydrocarbon hydroxyl primitives of connection, linear structure, aliphatic ring knot can be selected from Any one of structure, aliphatic heterocycle structure, aromatic ring structure and heteroaromatic structure appoint several structures.

Work as L₁、L₂In aliphatic ring structure, aliphatic heterocycle structure, aromatic ring structure and heteroaromatic structure It is any or when appointing several structures, the carbon atom that is connected with hydroxyl, which can participate in cyclization, can not also participate in cyclization.

Specifically, L₁、L₂It can be selected from following any or appoint several：Singly-bound or unsaturated bond, hetero atom linker, molecule Amount is residual more than the divalent of 1000Da or multivalence polymer chain no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight The divalent of base, molecular weight no more than 1000Da or polyvalent mineral small molecule chain residue, molecular weight are more than the divalent or more of 1000Da The inorganic macromolecular chain residue of valence.

Work as L₁、L₂When selected from singly-bound or unsaturated bond, it is selected from following any structure：Carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen Singly-bound, carbon-carbon double bond, aromatic radical；It is preferred that carbon-carbon single bond.What is formed is suitable as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Work as L₁、L₂When selected from hetero atom linker, it can be selected from following any or appoint several combinations：Ether, thioether group, Secondary amine, tertiary amine groups, silicon substrate, phosphorus base, triazole, isoxazole, triazine, ethylene ehter bond, amide groups, imide, thioamides It is base, enamine base, carbonate group, carbamate groups, thiocarbamate base, thioester substrate, ortho acid ester group, phosphate-based, sub- Phosphate-based, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl Base, thio secondary phosphoryl, phosphorus silane ester group, silane ester group, carbamide, thioamides, phosphamide, phosphoramidite, pyrophosphoramide, Cyclophosphamide, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, thioamides key, 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, 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, sulfinat, sulphur Amide groups, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide；L₁、L₂Preferably ether, thioether group, secondary amine, Tertiary amine groups, amide groups, carbonate group, carbamate groups, urea groups.What is formed is suitable containing single hydrocarbon hydroxy compounds (III) knot Structure is exemplified below：

Work as L₁、L₂When being no more than the divalent or multivalence small molecule alkyl of 1000Da selected from molecular weight, 1 to 71 are typically contained The valence state of a carbon atom, alkyl can be 2-144 valences, can contain heteroatom group, can be free of has heteroatom group.Briefly Say, the divalent or multivalence 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 or any by hydridization form：Two to one hundred four ten tetravalence C_1-71Alkyl, two to one hundred four ten tetravalence ring C_3-71 Alkyl, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred four ten tetravalence aryl；L₁、L₂It is preferred that two arrive tetravalence methyl, two Octavalence propyl is arrived to sexavalence ethyl, two, two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valence cyclopenta, two to ten Cyclohexyl radicals, two arrive sexavalence phenyl.What is formed is suitable as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Wherein, g is a fixed value or average value, g >=20.

Work as L₁、L₂Can be any appropriate when being more than the divalent or multivalence polymer chain residue of 1000Da selected from molecular weight Divalent or multivalence polymer chain residue include but are not limited to divalent or multivalence carbochain polymer residue, divalent or multivalence heterochain Polymer residue, divalent or element of multivalence organic polymer residue.Wherein, polymer can be homopolymer, or appoint several lists The copolymer of body, oligomer or polymer composition；Polymer chain can be flexible chain or rigid chain.

Work as L₁、L₂Can be that any appropriate macromolecular main chain is main when selected from divalent or multivalence carbochain polymer residue The polymer residue being made of carbon atom, can be selected from by it is any in the following group, any it is unsaturated in the form of, any quilt Substitution form is any by hydridization form：Divalent or multivalence polyolefins chain residue, as divalent or multivalence Polyethylene Chain are residual Base, 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 alcohol chain Residue, divalent or multivalence Polyvinylalkylethers chain residue, divalent or multivalence polybutadiene chain residue, divalent or the poly- isoamyl of multivalence Diene chain residue, divalent or multivalence polychlorobutadiene chain residue, divalent or multivalence polynorbornene chain residue etc.；Divalent or multivalence Polyacrylic chain residue, as divalent or multivalence polyacrylic acid chain residue, divalent or multivalence polyacrylamide chain residue, divalent or Multivalence polymethyl acrylate chain residue, divalent or multivalence polymethyl methacrylate chain residue etc.；Divalent or multivalence polyacrylonitrile Class chain residue, such as divalent or multivalence polyacrylonitrile chain residue.L₁、L₂It is preferred that divalent or multivalence Polyethylene Chain residue, divalent or more Valence polypropylene chains residue, divalent or multivalence polystyrene chain residue, divalent or multivalence polyvinyl chloride chain residue, divalent or multivalence are poly- Butadiene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polyacrylic acid chain residue, divalent or multivalence are poly- Acrylamide chain residue, divalent or multivalence polyacrylonitrile chain residue.What is formed is suitable containing single hydrocarbon hydroxy compounds (III) structure It is exemplified below：

Wherein, g, h, i, j, k are each independently a fixed value or average value, preferably g >=36, h >=36, i >=36, j ≥12、k≥12。

Work as L₁、L₂Can be that any appropriate macromolecular main chain is main when selected from divalent or multivalence heterochain polymer residue The polymer residue being made of the hetero atoms such as carbon atom and nitrogen, oxygen, sulphur, can be selected from it is any in the following group, any not Saturated 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, Divalent 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.；Two Valence or multivalence polyesters chain residue, such as divalent or multivalence polycaprolactone chain residue, divalent or the poly- valerolactone chain residue of multivalence, divalent Or multivalence polylactide chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence unsaturation are poly- Ester 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.. L₁、L₂It 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 Chain residue, divalent or multivalence polyurethane chain residue.What is formed is suitable as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Work as L₁、L₂Can be any appropriate macromolecular main chain when selected from divalent or element of multivalence organic polymer residue The polymer residue being mainly 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 By it is any in the following group, any it is unsaturated in the form of, 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 poly organo Alkane chain residue, divalent or multivalence poly-organosilicon borine chain residue, divalent or multivalence poly-organosilicon azane chain residue, divalent or multivalence Poly-organosilicon sulfane chain residue, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or the poly- organic metal siloxanes of multivalence Chain residue；Divalent or multivalence organic boron Type of Collective object chain residue, such as the divalent or poly- organo-borane chain residue of multivalence, divalent or multivalence Poly- organic boroxane chain residue, divalent or the poly- organic boron azane chain residue of multivalence, 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 are organic Lead Type of Collective object chain residue；Divalent or multivalence organic tin polymer chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain are residual Base；Divalent or multivalence antimony organic Type of Collective object chain residue.L₁、L₂It is preferred that divalent or multivalence poly-organosilicon alkane chain residue, divalent or more Valence polysiloxane chain residue, divalent or the poly- organo-borane chain residue of multivalence.What is formed is suitable containing single hydrocarbon hydroxy compounds (III) structure example is as follows：

Wherein, g, h, i, k are each independently a fixed value or average value, preferably g >=36, h >=36, i >=36, k >=12.

Work as L₁、L₂Can appoint when being no more than the divalent or polyvalent mineral small molecule chain residue of 1000Da selected from molecular weight Suitable molecular backbone and side chain anticipate mainly by the hetero atoms structure such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus At inorganic molecules chain residue, generally, the divalent or polyvalent mineral small molecule chain residue can be selected from in the following group Any, any unsaturated form, any substituted form or any by hydridization form：Divalent or multivalence silicon Alkane chain residue, divalent or multivalence silicon oxide compound chain residue, divalent or multivalence sulphur silicon compound chain residue, divalent or multivalence sulphur nitrogen Compound chain residue, divalent or multivalence phosphazene compound chain residue, divalent or multivalence phosphoric-oxygenic compound chain residue, divalent or multivalence Borine chain residue, divalent or multivalence boron-oxygen chain residue.L₁、L₂It is preferred that, divalent or multivalence silane chain residue, divalent or more Valence silicon oxide compound chain residue, divalent or multivalence phosphazene compound chain residue, divalent or multivalence borine chain residue.What is formed is suitable It is as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Work as L₁、L₂Can be arbitrary when being more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da selected from molecular weight Suitable macromolecular main chain and side chain are mainly by the hetero atoms structure such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus At inorganic macromolecular chain residue.

Wherein, L₁、L₂Can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form or It is any by hydridization form：Divalent or multivalence polysilane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence Polysulfide silicon chain residue, divalent or multivalence polysulfide nitrogen chain residue, divalent or multivalence polyphosphoric acid chain residue, divalent or multivalence polyphosphazene chain Residue, divalent or multivalence polychlorostyrene are residual for phosphonitrile chain residue, divalent or multivalence polyborane chain residue, divalent or the poly- boroxane chain of multivalence Base.L₁、L₂It is preferred that divalent or multivalence polysilane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence polyphosphazene chain Residue, divalent or multivalence polyborane chain residue.What is formed is suitable as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Wherein, g, h are each independently a fixed value or average value, preferably g >=36, h >=36.

L₁、L₂Also selected from any being modified with any inorganic macromolecular with residue in the following group or by surface Inorganic macromolecular with residue：Zeolite-type molecular sieves, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecular sieve, Buddha's warrior attendant Stone, graphite, graphene, graphene oxide, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, dioxy SiClx, silicon disulfide, silicon nitride, silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, pottery Porcelain, boron oxide, nitridation sulphur, calcium silicide, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, carbon Change boron, aluminium nitride, diaspore, gibbsite, corundum, titanium dioxide.L₁、L₂Preferably through the graphene of surface modification, by surface Modified carbon fiber, the silica being modified by surface, the silicon nitride being modified by surface, the silicon carbide being modified by surface, Silicate by surface modification, the glass fibre by surface modification, the boron nitride being modified by surface.What is formed suitably contains Single hydrocarbon hydroxy compounds is generally inorganic structure, and citing is such as：Silicon nitride, surface carbonization with silicone hydroxyl of the surface with silicone hydroxyl The glass fibre of silicate, surface with silicone hydroxyl of silicon, surface silica, surface with silicone hydroxyl with silicone hydroxyl.

Wherein, L₀For the linker between two single hydrocarbon hydroxyl primitives of connection, linear structure, aliphatic ring knot can be selected from Any one of structure, aliphatic heterocycle structure, aromatic ring structure and heteroaromatic structure appoint several structures；It is specifically selected Method is taken to refer to L₁、L₂Selection method, which is not described herein again；With L₁、L₂The difference is that L₀Skeletal atom there are two at least containing, shape At it is suitable as follows containing single hydrocarbon hydroxy compounds (III) structure example：

Wherein, g, h, i, j, k are each independently a fixed value or average value, preferably g >=36, h >=36, i >=36, j ≥36、k≥12。

In embodiments of the present invention, the compound (IV) containing silicone hydroxyl/silicone hydroxyl presoma, it is optional From but be not limited only to such as lower structure：

Wherein, K₅、K₆、K₇、K₈、K₉、K₁₀、K₁₁、K₁₂、K₁₃、K₁₄It is respectively independent for the group being connected directly with silicon atom Ground is selected from following any structure：Hydrogen atom, heteroatom group, molecular weight are no more than small molecule alkyl, the molecular weight of 1000Da Inorganic molecules chain residue, the molecular weight of polymer chain residue, molecular weight no more than 1000Da more than 1000Da is more than The inorganic macromolecular chain residue of 1000Da；A₁、A₂、A₃、A₄、A₅、A₆、A₇、A₈、A₉、A₁₀、A₁₁、A₁₂、A₁₃、A₁₄It is straight with silicon atom Connected hydrolyzable groups are connect, halogen, cyano, oxygen cyano, thiocyanogen, alkoxy, amino, sulfuric ester are included but are not limited to Base, boric acid ester group, acyl group, acyloxy, acylamino-, ketoxime base, alkoxide group, preferably halogen, alkoxy；Wherein, C7, C8, C9, Cyclic structure in C16, C17, C18 is the nonaro-maticity containing at least one silicone hydroxyl or armaticity sila cyclic group, and silicon is former Son is placed in cyclic structure, and cyclic structure can be small molecule ring, can also be macromolecular ring, is preferably 3~100 membered rings, More preferably 3~50 membered rings, more preferably 3~10 membered rings；The cyclization of cyclic structure in C7, C8, C9, C16, C17, C18 is former Son is each independently carbon atom, silicon atom or other hetero atoms, and at least one ring member nitrogen atoms are silicon atom and constitute silicon hydroxyl Base, and at least one ring member nitrogen atoms are connected with other atoms of compound；Cyclic structure in C7, C8, C9, C16, C17, C18 Hydrogen atom on each ring member nitrogen atoms can be substituted, and can not also be substituted；Ring-type in C7, C8, C9, C16, C17, C18 Structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；It indicates and changes Close the connection of other elements of object.

Wherein, the cyclic structure in C7, C8, C9, C16, C17, C18 can be selected from it is any in the following group, any not Saturated form, any substituted form or any by hydridization form：Sila cycloalkanes, sila cyclic hydrocarbon, cyclosiloxane, ring Silazane, cyclosilthiane, ring silicon phosphine, ring silicon borine, sila benzene, sila naphthalene, sila anthracene, sila phenanthrene, sila aromatic hydrocarbons；Listed The preferred silacyclopentan of cyclic structure, Silinane, sila cyclohexene, silacyclohexadiene, sila cyclonene, sila Benzene, cyclotrisiloxane, cyclotetrasiloxane, six siloxanes of ring, cyclotrisilazane, cyclotetrasilazane, six silazane of ring.The conjunction of formation Suitable compound (IV) structure example containing silicone hydroxyl/silicone hydroxyl presoma is as follows：

The structure of the compound (IV) containing silicone hydroxyl/silicone hydroxyl presoma of the example above is only that siliceous hydroxyl is better described The compound (IV) of base/silicone hydroxyl presoma with this condition possessed by typical structure and propose, only thus under the conditions of compare Some representational structures rather than limiting the scope of the present invention.

Wherein, when containing having described in two or more in the compound (IV) containing silicone hydroxyl/silicone hydroxyl presoma Any one of machine silicon structure primitive or when appointing several, can be connected with each other between each primitive, the connection by linker J Base J can be selected from following any or appoint several：Singly-bound, hetero atom linker, molecular weight are no more than the divalent or multivalence of 1000Da The divalent of small molecule alkyl, molecular weight more than 1000Da or multivalence polymer chain residue, molecular weight are no more than the divalent of 1000Da Or polyvalent mineral small molecule chain residue, molecular weight are more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da；

When J is selected from singly-bound, silicon silicon singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, silicon-carbon singly-bound, silicon can be selected from Nitrogen singly-bound；The preferred silicon silicon singly-bounds of J, carbon-carbon single bond, silicon-carbon singly-bound.What is formed is suitable containing silicone hydroxyl/silicone hydroxyl presoma Compound (IV) structure example is as follows：

When J 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；J is preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups.What is formed suitably contains silicone hydroxyl/silicon Compound (IV) structure example of hydroxyl groups precursors is as follows：

When J, which is selected from molecular weight, is no more than the divalent or multivalence small molecule alkyl of 1000Da, 1 to 71 carbon are typically contained The valence state of atom, 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 by it is any in the following group, any it is unsaturated in the form of, any quilt Substitution form is any by hydridization form：Two to one hundred four ten tetravalence C_1-71Alkyl, two to one hundred four ten tetravalence ring C_3-71Alkane Base, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred four ten tetravalence aryl；J preferably two arrives tetravalence methyl, two to six Valence ethyl, two arrive octavalence propyl, and two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valence cyclopenta, two to ten divalent Cyclohexyl, two arrive sexavalence phenyl.Suitable compound (IV) structure example containing silicone hydroxyl/silicone hydroxyl presoma formed is such as Under：

Wherein, g, h are each independently a fixed value or average value, g >=20, h >=20.

Can be any appropriate two when J, 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 J 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 alcohol chain residue, Divalent or multivalence Polyvinylalkylethers chain residue, divalent or multivalence polybutadiene chain residue, divalent or multivalence polyisoprene Chain residue, divalent or multivalence polychlorobutadiene chain residue, divalent or multivalence polynorbornene chain residue etc.；Divalent or multivalence poly- third Olefin(e) acid class chain residue, such as divalent or multivalence polyacrylic acid chain residue, divalent or multivalence 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.The preferred divalent of J or multivalence Polyethylene Chain residue, divalent or multivalence poly- third Alkene chain residue, divalent or multivalence polystyrene chain residue, divalent or multivalence polyvinyl chloride chain residue, divalent or multivalence polybutadiene Chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polyacrylic acid chain residue, divalent or multivalence polyacrylamide Amine chain residue, divalent or multivalence polyacrylonitrile chain residue.The suitable compound containing silicone hydroxyl/silicone hydroxyl presoma formed (IV) structure example is as follows：

When J 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..J 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.Suitable compound (IV) structure example containing silicone hydroxyl/silicone hydroxyl presoma formed is as follows：

Wherein, g, h, j, k are each independently a fixed value or average value, preferably g >=36, h >=36, j >=12, k >= 12。

Can be any appropriate macromolecular main chain master when J 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 boroxane chain residue, divalent or the poly- organic boron azane chain residue of multivalence, divalent or the poly- organic boron sulfane chain residue of multivalence, two Valence 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 organic tin polymer chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain residue； Divalent or multivalence antimony organic Type of Collective object chain residue.The preferred divalent of J or multivalence poly-organosilicon alkane chain residue, divalent or multivalence are poly- to be had Organic siloxane chain residue, divalent or the poly- organo-borane chain residue of multivalence.What is formed suitably contains silicone hydroxyl/silicone hydroxyl presoma Compound (IV) structure example it is as follows：

Can be arbitrary when J, which is selected from molecular weight, is no more than the divalent or polyvalent mineral small molecule chain residue of 1000Da Suitable molecular backbone and side chain are 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 divalent or polyvalent mineral small molecule chain residue can be selected to appoint in the following group A kind of, any unsaturated form, any substituted form or any by hydridization form：Divalent or multivalence silane Chain residue, divalent or multivalence silicon oxide compound chain residue, divalent or multivalence sulphur silicon compound chain residue, divalent or the nitridation of multivalence sulphur Close object chain residue, divalent or multivalence phosphazene compound chain residue, divalent or multivalence phosphoric-oxygenic compound chain residue, divalent or multivalence boron Alkane chain residue, divalent or multivalence boron-oxygen chain residue.The preferred divalent of J or multivalence silane chain residue, divalent or multivalence silica Compound chain residue, divalent or multivalence phosphazene compound chain residue, divalent or multivalence borine chain residue.What is formed suitably contains Compound (IV) structure example of silicone hydroxyl/silicone hydroxyl presoma is as follows：

Can be arbitrary conjunction when J, which is selected from molecular weight, is more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da Suitable macromolecular main chain and side chain is 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.

Wherein, J can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form or appoint It is a kind of by hydridization form：Divalent or multivalence polysilane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence are poly- Sulphur silicon chain residue, divalent or multivalence polysulfide nitrogen chain residue, divalent or multivalence polyphosphoric acid chain residue, divalent or multivalence polyphosphazene chain are residual Base, divalent or multivalence polychlorostyrene are residual for phosphonitrile chain residue, divalent or multivalence polyborane chain residue, divalent or the poly- boroxane chain of multivalence Base.The preferred divalent of J or multivalence polysilane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence polyphosphazene chain are residual Base, divalent or multivalence polyborane chain residue.Suitable compound (IV) structure containing silicone hydroxyl/silicone hydroxyl presoma formed It is exemplified below：

Wherein, g, h, i are each independently a fixed value or average value, preferably g >=36, h >=36, i >=36.

J is also selected from any inorganic macromolecular with residue or any carrying by surface modification in the following group The inorganic macromolecular of residue：Zeolite-type molecular sieves, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecular sieve, Buddha's warrior attendant Stone, graphite, graphene, graphene oxide, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, two Silica, silicon disulfide, silicon nitride, silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, stone English, ceramics, boron oxide, nitridation sulphur, calcium silicide, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, nitrogen Change boron, boron carbide, aluminium nitride, diaspore, gibbsite, corundum, titanium dioxide.Graphene that J is modified preferably through surface passes through The carbon fiber of surface modification, the silica being modified by surface, the silicon nitride being modified by surface, the carbon being modified by surface SiClx, the silicate being modified by surface, the glass fibre being modified by surface, the boron nitride being modified by surface.It is formed Suitably the compound (IV) containing silicone hydroxyl/silicone hydroxyl presoma is generally inorganic structure, and citing is such as：Surface carries silicone hydroxyl The silicic acid of silica, surface with silicone hydroxyl of silicon nitride, surface silicon carbide, surface with silicone hydroxyl with silicone hydroxyl Salt, surface carry the glass fibre of silicone hydroxyl.

In embodiments of the present invention, a compound can also contain dihydroxy primitive, single hydrocarbon hydroxyl primitive simultaneously With at least two in silicone hydroxyl/silicone hydroxyl presoma, namely primitive containing dihydroxy and single hydrocarbon hydroxyl primitive while containing two simultaneously Hydroxyl primitive and silicone hydroxyl/silicone hydroxyl presoma while containing simultaneously containing single hydrocarbon hydroxyl primitive and silicone hydroxyl/silicone hydroxyl presoma There are dihydroxy primitive, single hydrocarbon hydroxyl primitive and silicone hydroxyl/silicone hydroxyl presoma.This kind of compound can be included into compound (II), (III), any one of (IV), concrete structure just repeat no more here.

In embodiments of the present invention, at least one of various hydroxyl primitives and organic boronic are contained while described The compound (V) of primitive, wherein the selection method of organic boronic primitive can refer to organic boron acidic group in organoboron compound (I) The definition of member, which is not described herein again；Various hydroxyl primitives can be selected from dihydroxy primitive, single hydrocarbon hydroxyl primitive, silicone hydroxyl/silicone hydroxyl Presoma.The compound of formation can be selected from：Simultaneously the compound containing organic boronate member and dihydroxy primitive and meanwhile contain organic boron Acidic group member and the compound of single hydrocarbon hydroxyl primitive while compound containing organic boronate member and silicone hydroxyl/silicone hydroxyl presoma, Compound simultaneously containing organic boronate member and dihydroxy primitive and single hydrocarbon hydroxyl primitive while containing organic boronate member and dihydroxy The compound of base primitive and silicone hydroxyl/silicone hydroxyl presoma while the single hydrocarbon hydroxyl primitive of the member containing organic boronate and silicone hydroxyl/silicon The compound of hydroxyl groups precursors while containing organic boronate member and dihydroxy primitive and single hydrocarbon hydroxyl primitive and silicone hydroxyl/silicon hydroxyl The compound of base presoma.Its specific structure is no longer illustrated, and those skilled in the art can be with logic according to the present invention and arteries and veins Network is reasonably selected.

In embodiments of the present invention, the compound containing dynamic covalent bond He other reactive groups (VI), wherein dynamic covalent bond be selected from the organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key with And organic boronic acid anhydride key, the definition that method can refer to various dynamic covalent bonds is specifically chosen, which is not described herein again；Other reactions Property group can be a kind of, can also be a variety of.

In embodiments of the present invention, described not contain organic boronic primitive, various hydroxyl primitives and organic boron Acid esters key but compound (VII) containing other reactive groups, are not particularly limited its structure, any appropriate is free of There are organic boron acidic group, organic boronic ester group, various hydroxyl primitives and organic boronic ester bond but containing other reactive groups The optional compound (VII) as in the present invention of compound.

The present invention provides a kind of preparation method of the dynamic aggregation object based on combination dynamic covalent bond, the dynamic aggregation Object has line style or cyclic structure, preferably prepared by least one of following methods (but the present invention is unlimited In this)：

The first, participates in reaction by least following components and generates the acquisition of dynamic covalent bond key：At least one organoboration Object (I) is closed, at least two hydroxy-containing compounds are (selected from compound I and/or compound II and/or chemical combination containing organic boronate Object III and/or compound (IV), similarly hereinafter)；Wherein, organoboron compound (I), hydroxy-containing compounds contain at most two officials It can group；

The third, participates in reaction by least following components and generates the acquisition of dynamic covalent bond：At least one compound (V), Or itself and at least one organoboron compound (I) or at least two hydroxy-containing compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), organoboron compound (I), hydroxy-containing compounds contain extremely More Liang Ge functional groups.

The first, participates in reaction by least following components and generates the acquisition of dynamic covalent bond key：At least one organoboration Object (I) is closed, at least two hydroxy-containing compounds (are selected from compound (II)~(IV), similarly hereinafter)；Wherein, organoboron compound (I), At least one compound contains at least three functional groups in hydroxy-containing compounds, and a combination thereof does not generate the general of gel point or more Logical covalent cross-linking；

The third, participates in reaction by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one Kind compound (V), at least one compound (VII) or this two, at least one organoboron compound (I) or at least two Kind hydroxy-containing compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), Organoboron compound (I), hydroxy-containing compounds are containing at most Liang Ge functional groups and at least one compound (V) or organoboration It closes object (I) or hydroxy-containing compounds contains at least one other reactive group, and a combination thereof does not generate gel point or more Common covalent cross-linking.

The third, participates in reaction by least following components and generates dynamic covalent bond and the acquisition of common covalent bond：At least one It plants compound (V) or it contains at least one compound (VII) or at least one organoboron compound (I) or at least two Hydroxy compounds or at least one organoboron compound (I) and at least two hydroxy-containing compounds；Wherein, compound (V), organic Boron compound (I), hydroxy-containing compounds contain at least two functional groups, and at least one compound (V) or organic boron chemical combination Object (I) or hydroxy-containing compounds contain at least three functional groups, or at least one compound (V) or organoboron compound (I) Or hydroxy-containing compounds contain at least one other reactive group, and a combination thereof does not generate the common covalent of gel point or more Crosslinking；

It is used to prepare the dynamic aggregation object of combination dynamic covalent bond in the present invention, is not limited only to using above-described several Prepared by kind embodiment, can also be the combination of above-mentioned several embodiments or itself and other kind of embodiment.In every case Organoboron compound (I), hydroxy-containing compounds (II)~(IV), compound (V), compound (VI) is utilized to make in embodiments Prepare dynamic aggregation object for raw material, no matter it is in the form of raw material, or in the form of the compound of synthesis material, also Either in the form of the intermediate product of synthetic polymer, since it according to the present invention can instruct to be obtained, ought to include In the scope of patent protection of the present invention.Similarly, those skilled in the art according to the present invention can also instruct, reasonably Implement to obtain the dynamic aggregation object using above-mentioned several compounds.

In the dynamic aggregation object of the present invention, at least contain two classes dynamic covalently organic boronic ester bond, different types of dynamic Intensity, structure, dynamic, response and the formation condition of covalent organic boronic ester bond etc. are different, can reach collaboration again The orthogonal impact of performance；Also, it can be exchanged with each other and convert between each organic boronic ester bond under certain condition, make material Structure and performance have more adjustability.The dynamic response of organic boronic ester bond is strong in dynamic aggregation object, dynamic response mild condition. Compared to other existing dynamic covalent systems, the present invention take full advantage of organic boronic ester bond with good thermostabilization Property and high dynamic invertibity, can without catalyst, without high temperature, illumination or specific pH under conditions of realize dynamic aggregation object Synthesis and dynamic reversibility also reduce the limitation of use environment, extend polymer while improving preparation efficiency Application range.In addition, by optionally controlling other conditions (auxiliary agent, adjustment reaction temperature is such as added), Neng Gou Under appropriate environment, accelerates or be quenched dynamic covalent chemical balance, be at required state.

Ether ring mentioned in the present invention can be any ring containing ehter bond, and ring member nitrogen atoms are each independently Carbon atom, oxygen atom or hetero atom；The hetero atom can be selected from nitrogen-atoms, sulphur atom, phosphorus atoms, silicon atom, boron atom；Ether Hydrogen atom on ring ring member nitrogen atoms can be replaced by any substituent group, can not also be substituted；It can be single ring architecture, polycyclic Structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure.Generally, the ether ring includes but not limited to ring Oxidative ethane, tetrahydrofuran, oxinane, 1,4- dioxane, furans, crown ether etc.；The ether ring optimization ethylene oxide, tetrahydrochysene Furans.

The condensed ring being previously mentioned in the present invention can contain the contractings such as amido bond, ester bond, acid imide, acid anhydrides to be any The ring of the chemical bond formed is closed, and ring member nitrogen atoms are each independently carbon atom or hetero atom；The hetero atom can be selected from nitrogen Atom, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom；Hydrogen atom on condensed ring ring member nitrogen atoms can be taken by any Replace for base, can not also be substituted；It can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, Nested ring structure.Generally, the condensed ring includes but are not limited to lactone, lactide, lactams, cyclic imides, naphthenic acid Acid anhydride, cyclic peptide etc.；The preferred caprolactone of the condensed ring, lactide, caprolactam.

The relative molecular mass of term " molecular weight " used representative species in the present invention, for micromolecular compound, small For molecular radical and certain macromolecular compounds with fixed structure, macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And for oligomer, high polymer, oligomer residue, high polymer residue etc. have polydispersion The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the micromolecular compound in the present invention, small molecule Group refers in particular to the compound or group that molecular weight is no more than 1000Da；Macromolecular compound, that macro-radical refers in particular to molecular weight is big In the compound or group of 1000Da.

Heretofore described " organic group " refers to the base mainly constituted using carbon and protium as skeleton Group can be the small molecule group that molecular weight is no more than 1000Da, can also be the polymer chain that molecular weight is more than 1000Da Residue, suitable group citing is such as：Methyl, ethyl, vinyl, phenyl, benzyl, carboxyl, aldehyde radical, acetyl group, acetonyl etc..

Heretofore described " organosilicon radical " refers to mainly being constituted as skeleton using element silicon and protium Group can be the small molecule silylation that molecular weight is no more than 1000Da, can also be that molecular weight is organic more than 1000Da Silicon Type of Collective object chain residue, suitable group citing is such as：Silylation, siloxy group, silithiane base, silazane base etc..

Term " hetero atom " used refers to nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom in the present invention Etc. common non-carbon.

In the present invention, the carbon atom of any position is exchanged for heteroatoms the compound to be formed in hydrocarbon, is referred to as " miscellaneous hydrocarbon ".

Term " alkyl " used refers to the saturated hydrocarbyl for having straight or branched structure in the present invention.In appropriate situation Under, alkyl can have specified carbon atom number, for example, C_1-4Alkyl, the alkyl be included in linear chain or branched chain arrangement in have 1, 2, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tertiary butyl, n-pentyl, 2- methyl butyls, 3- methyl butyls, 4- methyl butyls, n-hexyl, 2- methyl amyls, 3- methylpents Base, 4- methyl amyls, 5- methyl amyls, 2- ethyl-butyls, 3- ethyl-butyls, heptyl, octyl, nonyl, decyl.

Term " naphthenic base " used refers to the cyclic hydrocarbon of saturation in the present invention.Cycloalkyl ring may include specified carbon atom number. For example, 3 to 8 yuan of naphthenic base include 3,4,5,6,7 or 8 carbon atoms.The example of suitable naphthenic base includes but not limited to ring third Base, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl.

Term " aryl " used means the monocycle or more of any stabilization of at most 7 atoms in each ring in the present invention Ring carbon ring, wherein at least one ring are aromatic.The example of such aryl includes but not limited to phenyl, xenyl, naphthalene, connection Naphthalene, tetralyl, indanyl, anthryl, dianthranide base, phenanthryl, connection phenanthryl.

Term " heteroaryl alkyl " expression monocycle of the stabilization of at most 7 atoms or more in each ring used in the present invention Ring, wherein at least one ring is aromatic series and at least one ring contains selected from hetero atoms such as O, N, S, P, Si, B.In this definition model Heteroaryl alkyl in enclosing includes but not limited to acridinyl, carbazyl, cinnoline base, quinoxalinyl, quinazolyl, pyrazolyl, indoles Base, benzotriazole base, furyl, thienyl, thiophenyl, 3,4- propylidene dioxies thiophenyl, benzothienyl, benzofuran Base, benzodioxan, benzo dioxine, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, imidazole radicals, pyrazinyl, Pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, tetrahydroquinoline, thiazolyl, isothiazolyl, 1,2,4- triazolyls, 1,2,3- triazoles Base, 1,2,4- oxadiazolyls, 1,2,4- thiadiazolyl groups, cyanuro 1,3,5,1,2,4- triazine radicals, 1,2,4,5- tetrazines base and four Oxazolyl.

For simplicity, the carbon atom number range in group is also labeled in the lower mark of C in the present invention with the form of subscripts It sets, indicates the carbon atom number that the group has, such as C_1-10It indicates with 1 to 10 carbon atom, C_3-20Indicate that there are 3 to 20 Carbon atom." undersaturated C_3-20Alkyl " refers to C_3-20Compound containing unsaturated bond in alkyl." substituted C_3-20Alkyl " refers to C_3-20The substituted obtained compound of the hydrogen atom of alkyl." the C of hydridization_3-20Alkyl " refers to C_3-20Carbon atom in alkyl is by miscellaneous original The compound that son substitution obtains.When a group can be selected from C_1-10When alkyl, any carbon in range shown in subscript can be selected from The alkyl of atomicity, you can be selected from C₁、C₂、C₃、C₄、C₅、C₆、C₇、C₈、C₉、C₁₀Any alkyl in alkyl.In the present invention, do not having In the case of having special instruction, indicate to can be selected from any integer within the scope of this with the subscript that range format marks, the range packet Include two endpoints.

For simplicity, also the symbology by one kind with continuous serial number with similar meaning uses "~" in the present invention It is attached, indicates that the mark content connected with "~" includes each symbology between serial number section, such as group R₁~R₃That indicate is group R₁, group R₂, group R₃；For another example that B1~B4 expressions is B1, B2, B3, B4.In this hair The symbology "~" occurred elsewhere in bright, represents such meaning.

It, all can be in the case of not specifying when the structure arrived involved in the present invention has isomer Any of which isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..

Heretofore described position isomery includes since substituent group, functional group or linking group in dihydroxy primitive or have The upper difference set of machine boric acid primitive and the position heterogeneous structure generated.

In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " A or more than one hydrogen atom can be replaced by any substituent group.In the case of being not particularly limited, substituent group therein It is not particularly limited.

For a compound, a group or an atom, can simultaneously be substituted and by hydridization, such as nitrobenzophenone Replace hydrogen atom, for another example-CH₂-CH₂-CH₂It is replaced by-CH₂-S-CH(CH₃)-。

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".

Be used to prepare compound (I)~(VII) of dynamic aggregation object, can be gas, liquid, crystal, powder, Grain, glue, paste etc..

During preparing dynamic aggregation object, organic boronic primitive in organoboron compound (I) with organic boric acid ester, Organic borate, organic halogen borine form in the presence of, with the hydroxy-containing compounds (compound (I) containing organic boronate And/or compound (II) and/or compound (III) and/or compound (IV)), during compound (V) reacted, can Hydrolyze to form organic boronic to first pass through, then with hydroxy-containing compounds (compound (I) containing organic boronate and/or compound (II) and/or compound (III) and/or compound (IV)), the hydroxyl elementary reaction in compound (V) form the dynamic Covalent bond；In the presence of organic boronic primitive in organoboron compound (I) is in the form of organic boric acid ester, can also directly it pass through Ester exchange reaction and hydroxy-containing compounds (chemical compounds I and/or compound II and/or compound III containing organic boronate and/ Or compound IV), the hydroxyl elementary reaction in compound (V) form new dynamic covalent bond.

For containing the compound (V) of at least two primitives in various hydroxyl primitives and organic boronic primitive, one simultaneously As need to enable by controlling reaction condition and the suitable reaction promoter of addition hydroxyl primitive in compound (V) with it is same Kind or the organic boronic primitive not contained in same compound (V) carry out only in polymer preparation process described in reaction formation Dynamic covalent bond, to obtain dynamic aggregation object.In one polymerization system, one or more kinds of compounds can be contained by removing (V) outside, one or more kinds of organoboron compounds (I) and/or one or more kinds of hydroxy-containing compounds can also be contained simultaneously (the compound I and/or compound II and/or compound III and/or compound IV of the member containing organic boronate).When raw material is selected from When compound (V), to ensure the stability of raw material, the organic boronic primitive in compound (V) is preferentially selected with organic boric acid ester Form exist.In view of compound (V) preparation and preservation process are comparatively complicated, it is accordingly used in preparing dynamic aggregation object Raw material components preferentially in organoboron compound (I) and hydroxy-containing compounds (chemical compounds I containing organic boronate and/or chemical combination Object II and/or compound III and/or compound IV) collocation selection is carried out in II.

In embodiments of the present invention, for organoboron compound (I), hydroxy-containing compounds (IIII)~(IV), change Object (V) is closed, form dynamic monomer and/or prepolymer and/or polymer during, in addition to using containing in compound Outside hydroxyl primitive and/or organic boronic primitive are reacted, other reactive groups that can be also contained simultaneously using it are optionally It is commonly covalently attached by polymerisation such as compound (VI) and/or compound (VII) with other compositions, it is common to react Constitute dynamic aggregation object.Organoboron compound (I), hydroxy-containing compounds (II)~(IV), compound (V) can also be participated in shape At prepolymer and/or polymer be blended with other compositions such as compound (VI) and/or compound (VII), then pass through other The common covalent linkage of ingredient forms dynamic aggregation object.It can also be initially formed common covalent linkage, re-form dynamic organic boronic Ester bond.

For compound (VI), generally by the phase between other reactive groups contained in compound (VI) Mutual reactance, or by other reactive groups contained in compound (VI) with compound (VII) and/or by organoboration Object (I), hydroxy-containing compounds (II)~(IV), compound (V) is closed to participate in contained in the prepolymer and/or polymer that are formed Reacting to each other between other reactive groups, to obtain the dynamic aggregation object containing dynamic covalent bond.Can also directly by Other reaction-ity group reactions that compound (VI) contains in itself form common covalent linkage.Certainly, the present invention not only limit and this, Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.

In embodiments of the present invention, other reactive groups can be common total by being obtained by the reaction for such as following form Valence link, to be formed together dynamic aggregation object with organic boronic ester bond：By containing in the amino and compound that contain in compound Some carboxyls carry out condensation reaction and form amido bond；Pass through the ammonia contained in the epoxy group and compound that contain in compound Base, sulfydryl carry out ring-opening reaction and form secondary amine key, thioether bond；Under the action of initiator or outer plus energy, by containing in compound Some alkylenes carry out free radical polymerization；In initiator or outside plus under the action of energy, by the alkylene that contains in compound into Row anion/cation polymerize；By the amino, hydroxyl, sulfydryl that contain in the isocyanate group and compound that contain in compound into Row reaction forms urea bond, urethane bond and thiocarbamate key；It is carried out by the epoxy group contained in compound Ring-opening polymerisation forms ehter bond；Under monovalence copper catalysis, pass through the alkynes contained in the azido group and compound that contain in compound Base carries out CuAAC reactions；Thiol-ene clicks are carried out by the alkylene contained in the sulfydryl and compound that contain in compound Reaction；Pass through the addition reaction etc. between the double bond that contains in compound；Wherein, it is preferably able at not higher than 100 DEG C quickly The mode of reaction is more preferably capable of the mode of fast reaction at room temperature, including but not limited to isocyanate group and amino, hydroxyl Base, the reaction of sulfydryl, acrylate reactions, thiol-ene click-reactions.

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 dynamic in the form of condensation polymerization When polymer, it can be implemented by polymerization techniques such as melt polymerization, polymerisation in solution, interfacial polymerizations；In another example working as compound When raw material obtains dynamic aggregation object in the form of free radical polymerization, bulk polymerization, polymerisation in solution, suspension polymerisation, breast can be passed through The polymerization techniques such as liquid polymerization are implemented；For another example when raw materials of compound obtains dynamic aggregation object in the form of ionic polymerization, It can be implemented by polymerization techniques such as polymerisation in solution, slurry polymerization, gas-phase polymerizations.

In preparation process, it is preferred to use solution polymerization process, emulsion polymerization technique prepare dynamic aggregation object.Described Solution polymerization process, emulsion polymerization technique, have can reduce system viscosity, be easy to mass-and heat-transfer, convenient for temperature control, can The advantage for avoiding hot-spot, the solution obtained, lotion are conducive to the operations such as be coated, mixed convenient for concentration or dispersion.

In the present invention, for the organic boronic primitive of composition dynamic aggregation object organic boronic ester bond, by boron atom institute The electron deficient having so that it easily generates bonding by nucleopilic reagent institute's attack containing unshared electron pair；And for structure At the various hydroxyl primitives of organic boronic ester bond, due to containing unshared electron pair on oxygen atom, with organic boron acidic group During member is in contact, organic boric acid ester key can be formed by reactions such as dehydration condensation, ester exchange reactions, to structure At dynamic aggregation object.Exactly dynamic reversibility possessed by organic boronic ester bond is utilized in the present invention, and dynamic aggregation object has been made.

In embodiments of the present invention, the dynamic aggregation object or its composition form can be solution, lotion, Cream, glue, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, Ionic liquid swell gel), foamed material etc., wherein the dissolvable small-molecular-weight contained in ordinary solid and foamed material at Point content is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Dynamic is poly- Shape and the volume for closing object ordinary solid are relatively more fixed, and intensity is high, and density is big, is suitable for the anti-explosion wall or instrument of high intensity Shell, while it also has good self-repairability and recuperability；Elastomer have elasticity and damping/energy absorption characteristics, also compared with For softness, self-repairability also higher；Dynamic aggregation object gel soft texture, there is preferable energy absorption capacity and elasticity, is suitable for preparing The energy-absorbing material of high-damping, while it also has good self-repairability and recuperability；Dynamic aggregation object foamed material is having When having the advantages of general foamed plastics such as density is low, light, specific strength is high, soft foam material also has good elasticity and energy-absorbing Property, in addition, dynamic aggregation object foamed material also has good self-repairability and recuperability simultaneously.

In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.

In the preparation process of dynamic aggregation object, mainly using mechanical foaming method, physical blowing method, three kinds of chemical blowing process Method foams to dynamic aggregation object.

Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be gelled, cures and become foamed material.For shorten molding cycle can be passed through air and be added emulsifier or Surfactant.

Wherein, the physical blowing method, be realized using physical principle in the preparation process of dynamic aggregation object it is poly- The foaming for closing object, generally comprises following four method：(1) inert gas blown method, i.e., inert gas under pressurized condition It is pressed into molten polymer or pasty material, then decompression heating, makes the gas expansion of dissolving and foam；(2) low boiling point is utilized Liquid evaporation gasification foaming, i.e., be pressed into low-boiling point liquid in polymer or under certain pressure, temperature regime, keep liquid molten Enter in polymer beads, then heat and soften polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching uses liquid Body medium, which immerses in polymer, dissolves the solid matter added in advance, makes to occur a large amount of holes in polymer and be in foaming Shape, such as by solable matter salt elder generation and mixed with polymers, after being shaped to product, then product is put and is located repeatedly in water Reason dissolves out solable matter to get to open-celled foam product；(4) hollow microsphere is added in hollow microsphere method in the plastic Become obturator-type foamed plastics by solidification；Wherein, preferably by dissolving in inert gas and low-boiling point liquid in the polymer Method foam.Using physical blowing method, have operation Poisoning smaller, foaming raw material cost is relatively low, and foaming agent is without residual The advantages that staying body.Further, it is also possible to be prepared using freeze-drying.

Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally comprise following two methods：(1) thermal decomposable foaming agent foaming utilizes chemical foaming agent The gas decomposed to give off after heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, that is, utilize hair The chemical reaction occurred between two or more components in foam system, generating inert gas (such as carbon dioxide or nitrogen) causes Polymer is expanded and is foamed.Polymerisation and foamable reaction balance carry out in order to control in foaming process, to ensure that product has preferably Quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by adding in the polymer The method of chemical foaming agent is added to foam.

In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to be molded dynamic aggregation object foamed material.

Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material is direct plungeed into die cavity to carry out foaming；Two-step method refers to first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam is molded ratio Two-step method is easy to operate and production efficiency is high, therefore it is preferred that one-step method carries out moulded from foam molding.

Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve In certain flow rate injecting material melt, then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent Under the action of form nuclei of bubbles.After expansion stage and solidifying and setting stage are all happened at full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while making foam solidifying and setting with the cooling of mold.

Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.Since it can not only realize continuous production, and it is more more competitive than injection-expansion molded in cost, because This is current most widely used foaming technology.

In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.

In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is half open-celled structure that leading to again, which has mutual disconnected structure then,.It, also can be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes：(1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be more than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.

In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are more than 0.4g/cm³, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm³, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm³, expansion ratio is more than 9.

Certain addible auxiliary agents, filler can also be added to collectively constitute dynamic in preparation process in dynamic aggregation object Polymer material, but these additives it is not necessary to.

In the preparation process of dynamic aggregation object material, the certain addible auxiliary agents being added can improve material Preparation process improves product quality and yield, reduces product cost or assign product certain distinctive application performance.Described Addible auxiliary agent is selected from following any or several auxiliary agents：Additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve helping for processing performance Agent, including lubricant, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation agent；Change table The auxiliary agent of face performance, including antistatic agent, emulsifier, dispersant；Change coloured light auxiliary agent, including colorant, fluorescent whitening agent, Delustering agent；Fire retardantization and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent.

Catalyst in the addible auxiliary agent can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst：① Polyurethane catalyst for synthesizing：Amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), four Methyl dipropylenetriamine, N, N- dimethyl cyclohexyl amines, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamines, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl- N-2- hydroxypropyls caproic acid, N, N- dimethyl benzylamines, N, N- dimethyl cetylamines etc.；Organometallic catalysts, as stannous octoate, Dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cycloalkanes Sour cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；2. gathering Catalysts for olefin synthesis：As Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, Aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, three second Amine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth Deng；3. CuAAC catalysts：Concerted catalysis is shared by monovalence copper compound and amine ligand；Monovalence copper compound can be selected from Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；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 butyl -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts：Photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyls phenylacetone, 2,2- dimethoxy -2- phenyl acetophenones etc.；Nucleopilic reagent catalyst, such as ethylenediamine, three Ethanol amine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used does not have It is particularly limited to, generally 0.01-0.5wt%.

Initiator in the addible auxiliary agent, can cause in polymerization process monomer molecule activate and Free radical is generated, reaction rate is improved, reaction is promoted to carry out, include but are not limited to following any or appoints several initiators： 1. radical polymerization shares initiator：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), two carbon of peroxidating Bis- (4- tert-butylcyclohexyls) esters of sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tert-butyl hydroperoxide Benzoic ether, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as Azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization Use initiator：Such as 2,2,6,6- tetramethyl -1- oxygroups piperidines, 1- chloro-1-phenyls ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator：Such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, butter of tin/alkyl halide system Deng；4. coordination polymerization initiator：Such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；⑤ Ring-opening polymerisation initiator：Such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, cause The preferred lauroyl peroxide of agent, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is without spy It does not limit, generally 0.1-1wt%.

Antioxidant in the addible auxiliary agent can delay the oxidation process of polymer material, ensure material It can be successfully processed and be extended its service life, include but are not limited to following any or appoint several antioxidant：By Hinder phenols, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) butane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl benzene Phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-terts Butylphenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros equal three Piperazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '- Two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, it is such as thio Dipropionic acid dilauryl, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, phosphorous acid Three nonyl phenyl esters, three [2.4- di-tert-butyl-phenyls] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butylhydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphorous Acid esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Institute Antioxidant dosage is not particularly limited, generally 0.01-1wt%.

Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyls； Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer Agent, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-t-butyls Benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, the positive fourth positive group dithiocarbamates first of N '-two Sour nickel etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, it is used Light stabilizer dosage be not particularly limited, generally 0.01-0.5wt%.

Heat stabilizer in the addible auxiliary agent, enable to polymer material during processing or use not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers：Lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide 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；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.

Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, second Third glue, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, Styrene-Butadiene-Styrene Block Copolymer etc..Wherein, toughener is excellent Select the third glue of second, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS), chlorinated polyethylene resin (CPE), toughener used Dosage is not particularly limited, generally 5-10wt%.

Lubricant in the addible auxiliary agent can improve material lubricity, 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；Fatty acid ester, such as fat Fat acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type, such as stearmide or tristearin Sour amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamides；Fatty alcohol and polyalcohols, it is such as stearic Alcohol, cetanol, pentaerythrite；Metal soap, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate. Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, lubricant quantity used is without spy It does not limit, generally 0.5-1wt%.

Releasing agent in the addible auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean, It includes but are not limited to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl Phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol etc.. Wherein, the preferred dimethicone of releasing agent, remover dosage used are not particularly limited, generally 0.5-2wt%.

Plasticizer in the addible auxiliary agent, can increase the plasticity of polymer material so that polymer Hardness, modulus, softening temperature and brittle temperature decline, and elongation, flexibility and flexibility improve comprising but be not limited only to Under it is any or appoint several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, adjacent benzene two Formic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, O-phthalic It is bis- (13) esters of sour butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, right Phthalic acid two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Aliphatic ester Class, 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, ring Oxygen 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, Dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat Acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, inclined benzene three Acid esters, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), Dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene Dioctyl phthalate diisodecyl ester (DIDP), tricresyl phosphate (TCP), plasticizer consumption used are not particularly limited, generally 5- 20wt%.

Foaming agent in the addible auxiliary agent, can so that polymer samples foam pore-forming, to obtain it is light, every Heat, sound insulation, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Physics is sent out Infusion, such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, fourth Alkane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as bicarbonate Sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two are sub- Nitro terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide formic acid Potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.

Dynamic regulation agent in the addible auxiliary agent, can promote the dynamic of dynamic aggregation object, be usually Either free carboxyl group or the compound of electronics pair can be provided or be received with free hydroxyl, include but are not limited to water, hydrogen Sodium oxide molybdena, alcohol, carboxylic acid, lewis base, lewis acid etc..The dynamic of polymer can be adjusted by adding this analog assistant, to obtain The expected performance that must be optimized, dynamic regulation agent dosage used are not particularly limited, generally 0.1-10wt%.

The deleterious charge assembled in polymer samples can be guided or disappeared by the antistatic agent in the addible auxiliary agent It removes, makes it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several antistatic Agent：Anionic antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, To nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, Fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, Dodecyl trimethylamine bromide；Amphoteric ion type antistatic agent, as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N- lauryls-N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, Alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, it is such as poly- Allyl amide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, antistatic The preferred lauryl trimethyl ammonium chloride of agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used do not have It is particularly limited to, generally 0.3-3wt%.

Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid comprising auxiliary agent Surface tension between phase is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any Kind appoints several emulsifiers：Anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid Sodium, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, Phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion Type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, as fatty alcohol polyoxyethylene ether, alkyl phenol are poly- Ethylene oxide ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythrite fat Acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecyl Benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used is without spy It does not limit, generally 1-5wt%.

Dispersant in the addible auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into carefully Small particle and be suspended in liquid, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms and stabilizes suspension comprising but be not limited only to following any or appoint several dispersants：It is cloudy Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as poly alkyl alcohol Ethylene oxide ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, it is such as bright Glue, water-soluble glue, lecithin, sodium alginate, lignosulfonates, polyvinyl alcohol etc..Wherein, the preferred detergent alkylate of dispersant Sodium sulfonate, naphthalene system methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether, dispersant dosage used do not limit especially It is fixed, generally 0.3-0.8wt%.

Colorant in the addible auxiliary agent can make polymeric articles show required color, increase Surface color and polish comprising but be not limited only to following any or appoint several colorants：Inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H₂G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc..Wherein, the selection of colorant need not be limited especially depending on color sample demand Fixed, colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.

Fluorescent whitening agent in the addible auxiliary agent can make contaminated substance obtain the sparkling of similar fluorite Effect comprising but be not limited only to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White agent CBS), bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-talan Base) dibenzoxazine (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.

Delustering agent in the addible auxiliary agent when incident light being enabled to reach polymer surfaces, occurs unrestrained anti- It penetrates, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents：Settle sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, the preferred titanium dioxide of delustering agent Silicon, delustering agent dosage used are not particularly limited, generally 2-5wt%.

Fire retardant in the addible auxiliary agent, can increase the flame resistance of material comprising but be not limited only to Under it is any or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic combustion inhibitor, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, tricresyl phosphate Phenyl ester, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, generally For 1-20wt%.

Nucleating agent in the addible auxiliary agent can accelerate crystallization speed by the crystallization behavior of change polymer Rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, improves the product transparency, surface The purpose of the physical mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but It is not limited only to following any or appoints several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, the preferred dioxy of nucleating agent SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1- 1wt%.

Rheological agent in the addible auxiliary agent can ensure that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, its redispersibility can be improved comprising but not only limit In following any or several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.

Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency, to meet various demands such as its stability and application performance during production, storage and use, packet It includes but is not limited only to following any or appoints several thickeners：Lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.

Levelling agent in the addible auxiliary agent can ensure that the flat smooth of polymer coating film is uniform, improve and apply Film surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Polyacrylate, Organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used are not particularly limited, generally 0.5-1.5wt%.

The addible filler, primarily serves following effect in the polymeric material：1. reducing molded article Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.

The addible filler, selected from following any or several fillers：Inorganic non-metallic filler, metal are filled out Material, organic filler.

The addible inorganic non-metallic filler includes but are not limited to following any or appoints several：Calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, fullerene, two Molybdenum sulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, Flyash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass are micro- Pearl, foam microspheres, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, metatitanic acid Calcium fiber, carbon silica fibre, ceramic fibre, whisker etc..

The addible metal packing includes but are not limited to following any or appoints several：Copper, silver, nickel, iron, Powder, nano particle and the fiber of gold etc. and its alloy.

The addible organic filler includes but are not limited to following any or appoints several：Fur, natural rubber Glue, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, enzyme, hormone, raw lacquer, wood powder, shell powder, wood Sugar, silk, artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..

Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber Glue, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.

In the preparation process of dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, thermostabilization Agent, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.The preferred calcium carbonate of addible filler, barium sulfate, talcum Powder, carbon black, glass microballoon, graphene, glass fibre, carbon fiber.

In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.

It, can be by any appropriate material hybrid mode known in the art by one in the preparation process of dynamic aggregation object Surely the raw material matched prepares dynamic aggregation object by mixing, and can be interval, semicontinuous or continuous processing form mixing； Similarly, interval also may be selected, semicontinuous or continuous processing form is molded dynamic aggregation object.The hybrid mode packet of use Include but be not limited only to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., wherein it is preferred that Solution is stirred, melting is stirred and melting extrusion.Energy in material mixed process provides form It is limited to heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, injection moulding, mould Molded, tape casting, calendering formation, cast molding.

The specific method for preparing dynamic aggregation object, the typically shape by raw material to dissolve or disperse are stirred using solution Formula is stirred mixing in the reactor in respective solvent or in common solvent.In general, hybrid reaction temperature controls At 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, time control is mixed in 0.5-12h, preferably 1-4h.It can incite somebody to action The product obtained after mixing is poured into suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0- 48h obtains polymer samples.Reservation solvent can be selected to be made with solution, emulsion, paste, glue during this as needed Etc. polymer samples existing for forms, or selection removes solvent and solid polymer sample existing for the forms such as membranaceous, blocky is made Product.

When preparing dynamic aggregation object material using the method as raw material using compound (VI), compound (VII), usually also It needs that initiator is optionally added in a solvent in a manner of polymerisation in solution to cause polymerization and obtains dynamic aggregation object, or be added Dispersant and oil-soluble initiator are configured to suspension and obtain dynamic in a manner of suspension polymerisation or slurry polymerization to cause polymerization Polymer, or addition initiator and emulsifier are configured to emulsion and obtain dynamically gathering to cause polymerization in a manner of emulsion polymerization Close object.Used polymerisation in solution, suspension polymerisation, slurry polymerization and emulsion polymerization method, be those skilled in the art Member is known and widely used polymerization, can be adjusted according to actual conditions, no longer be developed in details here.

Used solvent, should carry out according to actual conditions such as reactant, product and reaction process in above-mentioned preparation method Selection includes but are not limited to following any solvent or appoints the mixed solvent of several solvents：Deionized water, acetonitrile, acetone, fourth Ketone, benzene,toluene,xylene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, chloroform, dichloromethane, 1,2- dichloros The positive fourth of ethane, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone, isopropyl acetate, acetic acid Ester, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, phosphate buffer solution Deng；It is preferred that deionized water, toluene, chloroform, dichloromethane, 1,2- dichloroethanes, tetrahydrofuran, dimethylformamide, phosphoric acid are slow Rush solution.In addition, solvent is also selected from oligomer, plasticizer, ionic liquid；The oligomer includes but are not limited to poly- third Olefin(e) acid N-butyl oligomer, atoleine etc.；The plasticizer can be selected from class described in the plasticizer in addible auxiliary agent Not, which is not described herein again；The ionic liquid is generally made of organic cation and inorganic anion, and cation is usually alkane Base quaternary ammonium ion, alkyl quaternary see ion, the substitution of 1,3- dialkyl group imidazol ion, the alkyl-substituted pyridinium ions of N- etc.；The moon from Son is usually halide ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, also has CF₃SO₃ ^-、(CF₃SO₂)₂N^-、C₃F₇COO^-、 C₄F₉SO₃ ^-、CF₃COO^-、(CF₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₂F₅SO₂)₂N^-、SbF₆ ^-、AsF₆ ^-Deng.Wherein, deionization is utilized Water come prepare dynamic aggregation object and select retained when, hydrogel can be obtained；Dynamic aggregation is prepared using organic solvent Object simultaneously selects when being retained, and can obtain organogel；Dynamic aggregation object is prepared using oligomer and selects to be retained When, oligomer swell gel can be obtained；When preparing dynamic aggregation object using plasticizer and selecting to be retained, it can obtain Plasticizer swell gel；When preparing dynamic aggregation object using ionic liquid and selecting to be retained, ionic liquid can be obtained Swell gel.

In above-mentioned preparation method, the compound liquid concentration configured is according to the structure of selected reactant, molecular weight, dissolving Depending on degree and required dispersity, it is not particularly limited, preferred a concentration of 0.1~10mol/L of compound liquid, more preferably For 0.1~1mol/L.

The specific method for preparing dynamic aggregation object material is stirred using melting, it is typically that raw material is straight in the reactor It connects and is stirred reaction after being stirred or heating melting, such mode is generally gas, liquid or lower melting-point in raw material It is used in the case of solid.In general, the control of hybrid reaction temperature at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixes Mixing time control is closed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mold, At 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, 0-48h is placed, polymer samples are obtained.

When preparing dynamic aggregation object material using the method as raw material using compound (V), compound (VII), usually also It needs to be optionally added into a small amount of initiator and obtains dynamic aggregation object in a manner of melt polymerization or gas-phase polymerization to cause polymerization.Its The method of used melt polymerization, gas-phase polymerization, is well known to those skilled in the art and widely used polymerization side Method can be adjusted according to actual conditions, no longer be developed in details here.

It is mixed with the specific method of dynamic aggregation object material using melting extrusion, is typically to add the raw material into extruder In carry out extrusion blending reaction, extrusion temperature is 0-280 DEG C, preferably 50-150 DEG C.Reaction product can be cut out after direct tape casting At suitable dimension, either obtained extrusion sample is carried out to utilize injection molding machine or moulding press to carry out sample preparation after being crushed.Injection molding temperature Degree be 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature is 0-280 DEG C, preferably 25-150 DEG C, more preferable 25-80 DEG C, clamp time 0.5-60min, preferably 1-10min, the preferred 4-15MPa of molding pressure.It can be by batten It is placed in suitable mold, at 0-150 DEG C, under preferably 25-80 DEG C of temperature condition, places 0-48h, obtain final polymer-like Product.

In the preparation process of dynamic aggregation object material, selected organoboron compound (I), hydroxy-containing compounds (II) ~(IV), compound (V), compound (VI), compound (VII) can flexibly be held at component selections and formula rate, but be answered It is reasonably designed according to target material performance and the structure of selected compounds, the reactive group number contained and molecular weight And combination.Wherein, the organoboron compound (I) that is added, hydroxy-containing compounds (II)~(IV), compound (V), compound (VI), compound (VII) should ensure that the molar equivalent ratio of functional group and/or other reactive groups in reactant system is in Range appropriate.The dihydroxy primitive contained in organoboron compound (I), hydroxy-containing compounds (II)~(IV), compound (V) With range of the molar equivalent than preferably 0.1~10 of organic boronic primitive functional group, more preferable 0.3~3 range, more preferably 0.8~1.2 range.When the function contained in organoboron compound (I), hydroxy-containing compounds (II)~(IV), compound (V) The molar equivalent ratio of group is close to 1:When 1, the dynamic aggregation object that the extent of reaction is high, stability is good can be obtained；When organic boron chemical combination The molar equivalent for the functional group contained in object (I), hydroxy-containing compounds (II)~(IV), compound (V) is than deviateing 1:When 1, then It can obtain the preferable dynamic aggregation object material of dynamic.Similarly, anti-when selecting compound (VI), compound (VII) to be used as When component being answered to prepare dynamic aggregation object, the molar equivalent of other reactive groups is than also should be at model appropriate in reactant system It encloses, carries out range of the molar equivalent than preferably 0.1~10 of other reactive groups of polymerisation, more preferable 0.3~3 model It encloses, more preferable 0.8~1.2 range.In actual fabrication process, those skilled in the art can adjust according to actual needs It is whole.

In the present invention, the dynamic reversible of organic boronic ester bond in dynamic aggregation object and optional supermolecule hydrogen bond is utilized Property, when by external impacts, on the one hand polymer can show thickening response, on the other hand can also pass through organic boronic The reversible fracture of ester bond and hydrogen bond reaches multi-absorption and the dissipation to impact energy.For non-crosslinked system, thickening response production Raw complete viscous loss enhancing, plays strong energy absorption；And for dynamic crosslinking system, then it can generate viscosity-bullet Sex reversal can reduce the destruction of material while viscous loss.Therefore, by carrying out suitable component to dynamic aggregation object Selection and formula design, can prepare polymer fiber with excellent energy-absorbing effect, film, plank, elastomer, foam, Gel etc..Energy-absorbing is carried out using this dynamic aggregation object as energy-absorbing material, can embody good damping, damping, sound insulation, anti-impact The effects that hitting, to have extensive use in fields such as life, production, movement, leisure, amusement, military affairs, police service, security, medical cares On the way.In addition, the dynamic characteristic of organic boronic ester bond and optional supermolecule hydrogen bond, it is also possible that the dynamic aggregation object tool obtained There are good self-repairability, recuperability and reusability, extends its service life in energy-absorbing application process；Also It can be designed that the energy-absorbing material with shape memory function, be applied to specific occasion, such as the energy-absorbing protector of personalized customization. Energy-absorbing method provided by the present invention based on dynamic aggregation object, especially suitable for carrying out anti-impact to human body, animal body, article etc. Protection is hit, such as using the material as protector, body is protected in daily life, production and movement；It is prepared into anti- Quick-fried tent, blanket, wall, laminated glass, sound insulation deadener, sandwich plate etc. carry out explosive-proof protector to article；It is anti-to be prepared into other Article/apparatus is protected, airborne and air-drop protection, automobile collision preventing, electronic apparatus article defense of resistance to impact etc. is applied to.

Dynamic aggregation object of the present invention is described further with reference to some specific implementation modes.Specific implementation Example is present invention be described in more detail, non-limiting protection scope of the present invention.

Embodiment 1

34g acrylamides-phenyl boric acid-urethane copolymers are added in No. 1 reactor (with methyl isocyanate, N- (2- ethoxys) acrylamide is that carbamate monomer is made in raw material reaction；Again using AIBN as initiator, by acrylamide, 3- Acrylamido phenyl boric acid, carbamate monomer are obtained by free radical polymerization), 300mL deionized waters/THF mixed solvents, Be heated to 50 DEG C be stirred dissolving after, be slowly added to 1,1,3,3,5,5,7,7- prestoxs -1,7- of 3.5g, tetra- silica glycol and The polyglycereol methanol solution of 20mL0.3mol/L, and 2g graphenes are added, after ultrasonic disperse 40min, 2.5mL triethylamines are added, Continue to be stirred to react 2h under the conditions of 50 DEG C.Then be added 1.2g neopelexes, 0.7g bentonite, 0.5g stearic acid, 0.4g oleic acid, then be added wherein 0.4g organobentonites, 0.3g dimethyl silicone polymers, 0.2g dibutyl tin laurates, 41mg light stabilizers 770, heating stirring after mixing, obtain the grey black liquid with certain viscosity.To have certain viscous The solution example of degree is poured into suitable mold, sample is placed in 50 DEG C of baking ovens to dry removes solvent for 24 hours, is cooled to later It is placed at room temperature for 30min, finally obtains the membranaceous polymer samples of grey black.It is made into 80.0 × 10.0 × 0.02mm sizes Dumbbell shape batten carries out extension test using cupping machine, and rate of extension 10mm/min, measuring sample tensile strength is 3.89 ± 0.11MPa, elongation at break are 289 ± 23%；It is 2.45S/cm to measure its conductivity with four probes, in tensional state Under conductivity be 3.23S/cm.Thin polymer film shows good intensity, toughness, electric conductivity and stress response, is drawing The early period for stretching effect is different with the stress-strain diagram in later stage, is more dynamic than organic boronic cyclic ester key due to organic boronic estersil key State property is more preferable, and organic boronic estersil key is caused first to dissociate, and is dissociated after organic boronic cyclic ester key, realizes the dissipation step by step to energy, Improve the toughness of material.Sample is crushed after breaking, and fragment shape reclaimed materials is placed in 50 DEG C of mold presses 2- later It after 3h, can form a film again, and overall performance can reach original 90% or more, it can as one kind using its property Recyclability coating or protective film are used.

Embodiment 2

The polyol compound of 18.9mL is added in No. 1 reactor (using 4-Vinyl phenol, formaldehyde as raw material, by it 2- (methylol) -4-Vinyl phenol is synthesized for 24 hours with zinc nitrate hexahydrate reflux, then using methanol as solvent, triethylamine is catalysis It is made with four mercaptoacetate of pentaerythrite by mercaptan-alkene hydrocarbon click addition reactions for agent), 34mL 0.2mol/L The toluene solution of methyl phenyl silicone oil, the nano clay of 200 mesh of 1g and 0.2mg BHT antioxidant, first ultrasonic disperse 30min, so 150 DEG C are heated under stirring afterwards；Then 3.11g organoboron compounds are added (by propylene ylboronic acid and 1,3,5- triazines- 2,4,6- tri- mercaptan are made by thiol-ene click-reactions), 0.7mL triethylamines, after the reaction was continued at 150 DEG C 40-60min, Continue after reacting 1h under the conditions of nitrogen protection, is poured into suitable mold, and sample is placed in 80 DEG C of vacuum drying ovens It is further reacted for 24 hours, is cooled to is placed at room temperature for 30min later, finally obtain block-like stiff polymer material, polymerize Object sample surfaces are smooth, and have glossiness, it is left rear sample from the place of 1.5m high can still keep original state, have good Surface strength and rigidity.It is crushed and is placed in 80 DEG C of molds after placement 5h, sample can be molded again.It is made into 80.0 The dumbbell shape batten of × 10.0 × 2.0mm sizes, using cupping machine carry out extension test, rate of extension 10mm/min, It is 11.23 ± 0.54MPa to measure sample tensile strength.It is different in the early period of stretching action and the stress-strain diagram in later stage, be Since organic boronic estersil key is more preferable than the dynamic of organic boronic cyclic ester key, organic boronic estersil key is caused first to dissociate, it is organic It is dissociated after boric acid cyclic ester key, realizes the dissipation step by step to energy, improve the toughness of material.The polymer samples broken are recycled Afterwards, applying good pressure and be placed in 60 DEG C of vacuum drying oven heating and place 1-3h, section can be bonded voluntarily, is molded again, at Properties of sample after type reaches the 89% of raw sample.Utilize its plasticity, reusability and recuperability etc. Characteristic can be used as transparent organic polymer product and be used.

Embodiment 3

Acrylamide-boric acid ester copolymer of 34mL 0.4mol/L is added in No. 1 reactor (with 1- amino-ethyl boron Sour diisopropyl ester, acryloyl chloride are that raw material reaction is made borate acrylamide monomer, then by itself and N, N- dimethyl allene acyls Amine obtains final product by free radical polymerization) it is dissolved in the solution being configured in deionized water and a small amount of acetic acid, mixing is equal After even, being slow added into the polybutadiene that 5g chlorosilanes block, (with terminal hydroxy group 1,3- polybutadiene, dichlorodimethylsilane are original Material, toluene is solvent, with triethylamine absorbing reaction generate HCl be made) and the polyethylene glycol of 19.2mL 0.4mol/L it is water-soluble Liquid after being stirred 30min, is added the triethylamine of 3mL, is reacted under nitrogen protection counterflow condition, after heating reaction 3h, 0.3g titanium alloy powders, 0.5g ceramic powders, 0.2g calcium sulfate is added, after stirring evenly, the reaction was continued 4h.It is later that polymer is molten Liquid is poured into suitable mold, is placed in 50 DEG C of baking ovens to place and is dried and further reacts for 24 hours, and block is finally obtained The polymer samples of shape.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, is drawn using cupping machine Stretching test, rate of extension 10mm/min, it is 3.67 ± 0.31MPa to measure sample tensile strength, elongation at break is 286 ± 27%.Polymer samples surface obtained is smooth, has good intensity, can be stretched in a certain range.In addition, by sample After product surface carries out small cut, it is placed in 80 DEG C of mold after applying certain pressure fitting 1-3h, cut disappears, and has good Good selfreparing effect can be applied to and make shock resistance ground cushion.

Embodiment 4

The tetrahydrofuran solvent of 100mL, the poly dimethyl of 18g hexamethylene boron compounds sealing end are added in No. 1 reactor Silicone oil is (logical with the polydimethyl siloxane fluid (molecular weight is about 3000) of dibromo sealing end by it using 3- aminocyclohexanes boric acid as raw material Hydrocarbyl reaction is crossed to be made), in the state of stirring, 2.15g isopropyls ylboronic acid, 9mL modified hydroxyl silicon fully is added after dissolving Oil (using cyanuric acid, the chloro- 1- hexenes of 6- as raw material, the olefinic monomer of hydrogen bonds group is obtained by the reaction under potassium carbonate catalysis, then Its methyl hydrogen hydroxy silicon oil for being 20,000 with molecular weight is carried out Si―H addition reaction to be made under Pt catalytic conditions) and 2mL tri- Ethamine, continuation react 4h under the conditions of nitrogen protection.During the reaction, solution viscosity constantly rises, and after the completion of reaction, will gather Polymer solution pours into suitable mold, is placed in 80 DEG C of vacuum drying ovens to dry and removes solvent for 24 hours, is cooled to is placed at room temperature for later 30min finally obtains the blocky polymer solids sample in hard colloidal state.It is made into 80.0 × 10.0 × 2.0mm sizes Dumbbell shape batten carries out extension test using cupping machine, and rate of extension 10mm/min, measuring sample tensile strength is 2.18±1.12MPa.After the polymer samples broken are recycled, applies good pressure and be placed in 60 DEG C of vacuum drying oven and heat 2-3h is placed, section can be bonded voluntarily, is molded again, and properties of sample after molding reaches the 82% of raw sample.It can be by polymer Product is applied to the sealing of building filleting, the encapsulation process of electronic component as gasket seal.

Embodiment 5

Taking 20g phenyl boric acids modified silicon rubber, (using methyl vinyl silicone rubber, 2-MEA as raw material, triethylamine is to urge Agent, by mercaptan-alkene hydrocarbon click addition reactions be made intermediate product after, then with 2- formyl butylcyclohexane boric acid neopentyl glycols Ester obtains final product by Petasis reaction synthesis), the silanol-modified silicon rubber of 20g is (with methyl silicone rubber, γ-mercapto propyl first Base dihydroxy base silane is that raw material under the conditions of ultraviolet light, is added using DMPA as photoinitiator by mercaptan-alkene hydrocarbon click After intermediate product is made at reaction, then hydrolyze to obtain final product) and acrylic acid-acrylamide copolymer containing dihydroxy (with AIBN is initiator, and N- (2- (3,4- dihydroxy butylcyclohexyl) ethyl) acrylamide is copolymerized with acrylic acid by free radical polymerization Obtain) be added to and carry out mixing 30min in small-sized internal mixer after, 12g white carbons, 17g titanium dioxides, the oxidations of 3.2g tri- two is added Iron, 3g carbon nanotubes, 0.05g silicone oil continue to be kneaded 6h, after so that additive is sufficiently mixed uniformly with sizing material, sizing material are taken out, is set It in suitable mold, 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 later 30min is removed from the molds sample, and finally obtaining soft dynamic plugging glue material can foundation with good plasticity Die size is prepared into product of different shapes, while possessing excellent toughness, measures this material in no pulling force or pressure Possess different conductivity under force effect, illustrates that it also has stress response.In addition, its to possess a large amount of dynamic key very square Just it is recycled or waste processing applies good pressure and be placed in 60 DEG C after recycling the polymer samples broken Vacuum drying oven in heating place 1-3h, section can bond voluntarily, be molded again, and properties of sample after molding reaches raw sample 90%.Using its functional characteristic, silicon rubber damping shim can be made into applied to strain gauge, electronics Electrically, the fields such as medical instrument, auto industry.

Embodiment 6

It takes a certain amount of polyol compound to be dissolved in the solution for being configured to 0.2mol/L in toluene solvant, and therefrom takes 10mL Sample is added in No. 1 reactor, adds the BHT antioxidant of 3mg；1,8- dihydroxy-anthracenes are dissolved in toluene solvant, are matched It is set to the solution of 0.2mol/L, and 10mL samples is therefrom taken to be added in No. 1 reactor.In the state of stirring, 16g is added The double boric acid of Isosorbide-5-Nitrae-phenylene, are reacted under the conditions of 80 DEG C, and with the progress of stirring, solution viscosity rises, then will polymerization Object sample is poured into suitable mold, evaporates desolventizing 12h at room temperature.Later, polymer samples are flat on 80 DEG C After removing remaining solvent in vacuum drying oven, obtained polymer samples have larger rigidity, but quality is more crisp.It is made into The dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes carries out extension test, rate of extension 10mm/ using cupping machine Min, it is 6.32 ± 0.29MPa to measure sample tensile strength, and elongation at break is 42 ± 6%.The polymer samples broken are returned After receipts, applying good pressure and be placed in 60 DEG C of vacuum drying oven heating and place 2-3h, section can be bonded voluntarily, is molded again, Properties of sample after molding reaches the 80% of raw sample, using its property can as a kind of recuperability rigid gasket into It exercises and uses.

Embodiment 7

A certain amount of 1,7- heptandiols are taken to be dissolved in the solution for being configured to 0.4mol/L in methanol solvate；Take a certain amount of contain Dihydroxy primitive compound (II) (using tetraallyloxyethane, 3- sulfydryls -1,2-PD as raw material, methanol is solvent, three Ethamine is catalyst, is made by mercaptan-alkene hydrocarbon click addition reactions) it is dissolved in methanol solvate and is configured to 0.2mol/L's Solution；Respectively take compound (II) solution of the primitive containing dihydroxy of 20mL, 25g boric acid graft modification polypropylene (with peroxidating two Isopropylbenzene is initiator, with modified by maleic acid anhydride graft low-molecular-weight polypropylene；Then using p-methyl benzenesulfonic acid as catalyst, 1- is used Amino-ethyl boric acid reacts to obtain final product with maleic anhydride inoculated polypropylene), 50g polyacrylic acid N-butyls oligomer, 5g it is fine The plain nanocrystal of dimension is added in No. 1 reactor, is slowly stirred at ambient temperature, molten after stir about 40-50min Liquid starts, with certain viscosity, at this time to pour into sample in suitable mold, is cooled to is placed at room temperature for 30min later, final To the oligomer swell gel dynamic aggregation object sample of transparent membrane.It is made into the mute of 80.0 × 10.0 × 0.02mm sizes Bell pattern item carries out extension test using cupping machine, and rate of extension 50mm/min, it is 6.32 to measure sample tensile strength ± 0.76MPa, fracture percentage of elongation are 468 ± 25%.Thin polymer film soft texture has good intensity and toughness, can be Extend in a certain range, and there is good tear resistance.After the polymer samples broken are recycled, apply good Pressure is placed in heating in 60 DEG C of vacuum drying oven and places 2-3h, and section can be bonded voluntarily, is molded again, properties of sample after molding Reach the 84% of raw sample.This material can repeat recycling and use, and can be packed as a kind of recuperability using its property Film or pad pasting are used with product.

Embodiment 8

Take a certain amount of acrylamide-dihydroxy primitive copolymer (using 4-Vinyl phenol, formaldehyde as raw material, by its with Zinc nitrate hexahydrate reflux synthesizes 2- (methylol) -4-Vinyl phenol for 24 hours, then using AIBN as initiator, by 2- (methylol) - 4-Vinyl phenol is copolymerized to obtain with N,N-DMAA by free radical polymerization) it is dissolved in deionized water, it configures At the solution of 0.2mol/L；It (is original with 4-Vinyl phenol, acrylamide to take a certain amount of acrylamide-phenolic hydroxyl group copolymer Material, is that initiator is polymerized with AIBN, the amino in copolymer is then obtained product with ethyl di-isocyanate reaction) it is molten Solution is configured to the solution of 0.2mol/L in deionized water.Respectively take 20mL acrylamide-dihydroxy primitive copolymer solution and Acrylamide-phenolic hydroxyl group copolymer solution is added in No. 1 reactor and stirs by mixing, and after stirring 20-30min, adds Enter 15g borates modified polystyrene (using AIBN as initiator, using styrene and 4- vinylphenylboronic acid propylene glycol esters to pass through It is free-radical polymerized to be made), the nano silicon dioxide of 50mg grain sizes 25nm and 150mL toluene solvants, ultrasonic echography disperses 40min Afterwards, be warming up to 60 DEG C dissolved by stirring after, be added a small amount of 20% acetic acid aqueous solution the reaction was continued 4h, finally obtain block Shape hydrogel dynamic aggregation object, with good mechanical strength, elasticity and toughness are poor.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm sizes carries out extension test using cupping machine, and rate of extension 10mm/min measures sample Tensile strength is 13.75 ± 1.23MPa, and elongation at break is 98 ± 5%, after the polymer samples broken are recycled, is applied good Good pressure is placed in heating in 60 DEG C of water-bath and places 2-3h, and section can be bonded voluntarily, is molded again, properties of sample after molding Reach the 86% of raw sample.This material possesses good mechanical property and recuperability, can be as one kind using its property Orthopaedics corrects product and uses.

Embodiment 9

150mL chloroform solvents are added in No. 1 reactor, leads to nitrogen and removes water deoxygenation 1h, 13.2g partial hydrolysis is then added Borate modified polybutadiene (with Amino End Group 1,3- polybutadiene, (bromomethyl) boric acid diisopropyl ester are raw material, pass through hydrocarbon After intermediate product is made in glycosylation reaction, then propionamide is using DMPA as photoinitiator with 3- amino-N- (2- mercaptoethyls), in purple Under the conditions of outer light irradiation, by mercaptan-alkene hydrocarbon click addition reactions, the amino isopropyl isocyanate in the product of gained is anti- Answer, finally reaction product be placed in the deionized water of certain temperature and carry out partial hydrolysis and be made), the ethylene-vinyl alcohol of 32g it is total Itself and hydrobromic acid (using 1- hydroxyl boron heterocycle propylene as raw material, are passed through addition by polymers, 26mL 0.4mol/L organoboron compounds The bromo- 1- hydroxyls boron heterocycle propane of 2- is made in reaction；With 1,3,5- triacryl hexahydro -1,3,5- triazines, 2- aminoothyl mercaptans For raw material, AIBN is initiator, and triethylamine is catalyst, by thiol-ene click-reactions be made intermediate product after, then with 2- Bromo- 1- hydroxyls boron heterocycle propane is made by hydrocarbyl reaction) tetrahydrofuran solution, 3.2g graphenes and a small amount of 20% acetic acid water Solution after being stirred evenly under the conditions of 50 DEG C, then is added dropwise to 2mL triethylamines, the reaction was continued 4h.Then reaction solution is poured into properly Mold in, be placed in 60 DEG C of vacuum drying ovens and further reacted and dried for 24 hours, be cooled to be placed at room temperature for 30min later, Gelatinous polymer material is finally obtained, sample has good elasticity and toughness, can extend in wide range.By its The dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes is made, carries out extension test using cupping machine, rate of extension is 10mm/min, it is 5.32 ± 0.36MPa to measure sample tensile strength, and elongation at break is 447 ± 34%；It is measured with four probes Conductivity is 2.78S/cm, and conductivity in a stretched state is 4.35S/cm.Thin polymer film shows rubber property, has Good toughness, electric conductivity and stress response, in addition, product obtained also has good plasticity, it can be according to practical need It is positioned in mold of different shapes, and slightly applies certain stress under the conditions of certain temperature, you can be molded according to mold For polymeric articles of different shapes.After the polymer samples broken are recycled, apply the vacuum that good pressure is placed in 60 DEG C 2-3h is placed in heating in baking oven, and section can be bonded voluntarily, is molded again, and properties of sample after molding reaches the 85% of raw sample. In the present embodiment, polymer can be made to resilience washer, strain gauge or buffering spacer to use.

Embodiment 10

Acrylamide-halogen borine copolymer of the partial hydrolysis of 13g is added in No. 1 reactor (with 1- amino-ethyl boron Sour diisopropyl ester, acryloyl chloride are that borate acrylamide monomer 1 is made in raw material reaction；With isocyanates ethyl acrylate, second Amine is that monomer 2 is made in raw material reaction；Monomer 1, monomer 2 finally will with N,N-DMAA by free radical polymerization Product is placed in the deionized water Partial hydrolysis under certain temperature, obtains final product), 80mL toluene, stirred at 60 DEG C to It is completely dissolved, the polyethylene that 10mL 0.3mol/L dihydroxy primitives sealing end is then added is (poly- with Zr-FI catalyst ethylene Itself and 3- sulfydryls -1,2-PD then are passed through mercaptan-alkene hydrocarbon click addition reactions by symphysis at the polyethylene of ethenyl blocking Be made, wherein addition reaction catalyst is triethylamine) toluene solution, 0.5g carbon nanotubes, 3.3g 1,5-PDs, at 60 DEG C The reaction was continued in water-bath 4h.Solution example with certain viscosity is poured into suitable mold, room temperature is cooled to later and puts 30min is set, transparent organogel dynamic aggregation object sample is finally obtained.It is cut into the mute of 80.0 × 10.0 × 0.02mm sizes Bell pattern item carries out extension test using cupping machine, and rate of extension 50mm/min, it is 2.56 to measure sample tensile strength ± 0.23MPa, elongation at break are 345 ± 35%.The organogel is tough and tensile and soft, has both good toughness, can carry out compared with The extension and stretching of big degree measure this material and are gathered around under no pulling force or pressure effect while possessing excellent toughness There is different conductivity, illustrates that it also has stress response.In addition, after sample is broken, place it in 50 DEG C of mold The new sample for possessing 93% comprehensive performance of raw sample is can be obtained after fitting 3h, this material can be used as strain gauge into enforcement With.

Embodiment 11

Be added in No. 1 reactor 15mL 0.2mol/L dendritic polyol compounds (using methanol as solvent, three second Amine is catalyst, and by triallylamine and 1, production among level-one is made by mercaptan-alkene hydrocarbon click addition reactions in 2- dithioglycols After object, then continues through mercaptan-alkene hydrocarbon click addition reactions with triallylamine and two level intermediate product is made, later again with 1, Three-level intermediate product is made by mercaptan-alkene hydrocarbon click addition reactions in 2- dithioglycols, then is reacted with triallylamine and be made four Grade intermediate product, finally with 3- sulfydryls -1,2-PD pass through mercaptan-alkene hydrocarbon click addition reactions be made final product) first Benzole soln, 50mL 0.1mol/L are modified polynorbornene and (using vinyl boronic acids, cyclopentadiene as raw material, pass through DielR- Boric acid modified norbornene is made in Alder reactions；After vinylamine is reacted with carbethoxyl group isocyanates, then with cyclopentadiene The norbornene that amoyl modified is made is reacted by Diels-Alder；By boric acid modified norbornene, amoyl modified Norbornene, using metallocene catalyst/methylaluminoxane as catalyst system and catalyzing, is made most with norbornene by polyaddition reaction Final product) o-dichlorobenzene solution, the ester modified polybutadiene of 7.2g boric acid is (with Amino End Group 1,3- polybutadiene, (bromo first Base) boric acid diisopropyl ester is raw material, be made by hydrocarbyl reaction), the nanoclay of 200 mesh of 0.7g.Ultrasonic echography disperses After 40min, after being stirred evenly under the conditions of 60 DEG C, a small amount of 1mol/L NaOH solutions are added dropwise to, continue to stir under the conditions of 60 DEG C It mixes.After being slowly stirred about 30-40min, solution example is poured into suitable mold, sample is placed in 50 DEG C of baking ovens and is dried Solvent is removed for 24 hours, is cooled to is placed at room temperature for 30min later, is made into the dumbbell pattern of 80.0 × 10.0 × 2.0mm sizes Item, using cupping machine carry out extension test, rate of extension 10mm/min, measure sample tensile strength be 7.24 ± 0.34MPa, elongation at break are 734 ± 57%.It is different in the early period of stretching action and the stress-strain diagram in later stage, be due to Organic boronic acid anhydride key is more preferable than the dynamic of organic boronic cyclic ester key, causes after hydrogen bond dissociates, and organic boronic acid anhydride key first dissociates, It is dissociated after organic boronic cyclic ester key, realizes the dissipation step by step to energy, improve the toughness and energy absorption capacity of material.The polymerization that will be broken After the recycling of object sample, applies good pressure and be placed in 60 DEG C of vacuum drying oven heating and place 2-3h, section can be bonded voluntarily, weight New molding, properties of sample after molding reach the 88% of raw sample.In the present embodiment, polymer samples can be made a kind of close Sealing or recuperability elastic pellet toy are used, and can embody good toughness and elasticity, and can be according to need It is pressed into the product of different shape size, sample that is damaged or no longer needing may be recovered, new product is made and uses.

Embodiment 12

24g boric acid Grafted Polyethylene is taken (using ethylene-vinyl alcohol copolymer as raw material, it to be reacted with acryloyl chloride It obtains side chain and contains the ethylene copolymer of double bond, then itself and 2- sulfydryl second pinacol borates are passed through into thiol-ene click-reactions Be made), 22g boric acid lists sealing end polyethylene oxide (ethylene methacrylic ylboronic acid and 2 mercapto ethanol are clicked by thiol-ene After reaction, using boron trifluoride ether as catalyst, cause epoxyethane ring-expansion polymerization after using monochloro methane block be made), 32g Macromolecular list alkanol compounds (are reacted, by product and 3- butene-1-ols and propylene by 3- butene-1-ols and isopropyl isocyanate Sour methyl esters carries out free radicals copolymerization reaction under initiator A IBN effect and is made), 1.3g fire retardant TPP, 0.6g antimony oxide, 0.8g stearic acid, 0.1g irgasfos 168s, 0.1g antioxidant 1010s, 0.2g di-n-butyltin dilaurates, 0.5g dimethicones After mixing, it is added in small-sized extruder and carries out extrusion blending, extrusion temperature is 130-150 DEG C, obtained extrusion batten After being granulated, sample preparation is carried out using small injecting machine, injection temperature is 140-150 DEG C, then by thin slice batten obtained It is placed in 90 DEG C of bucks and is polymerize, then take out, be placed in mold, 4-6h is placed under the conditions of 120 DEG C of nitrogen protections and is carried out Dry and further reaction, finally obtains the dynamic aggregation object sample with flame retardant property.It is made into 80.0 × 10.0 The dumbbell shape batten of × 2.0mm sizes carries out extension test using cupping machine, and rate of extension 10mm/min measures sample Product tensile strength is 4.68 ± 0.35MPa, and elongation at break is 495 ± 64%.After the polymer samples broken are recycled, apply Good pressure is placed in heating in 60 DEG C of vacuum drying oven and places 1-2h, and section can be bonded voluntarily, is molded again, sample after molding Moral character can reach the 87% of raw sample.In the present embodiment, modeling can be applied to using polymer samples as a kind of flame-retardant additive Expect machine-shaping.

Embodiment 13

Be added in No. 1 reactor 18g phenyl boric acids modified polycarbonates (limonene oxide is extracted from orange peel, by its with Under the catalytic action of beta-diimine zinc polymerisation occurs for carbon dioxide, obtains makrolon PLimC, then by itself and [4- (mercaptos Ylmethyl) phenyl] boric acid neopentyl glycol ester and 6- aminothiouracils by thiol-ene click-reactions, then will be in product Amino and hydroxyl reacted with isopropyl isocyanate be made), the surfaces 0.5g carry silicone hydroxyl nano silicon dioxide, 5.3g acryloyls Itself and zinc nitrate hexahydrate reflux (using 4-Vinyl phenol, formaldehyde as raw material, are synthesized 2- by amine-dihydroxy primitive copolymer for 24 hours (methylol) -4-Vinyl phenol, then using AIBN as initiator, by 2- (methylol) -4-Vinyl phenol and N, N- dimethyl Acrylamide is copolymerized to obtain by free radical polymerization), the boric acid modified polystyrene of 7.2g (using AIBN as initiator, utilize benzene Ethylene and 4- vinylphenylboronic acids pass through free-radical polymerized be made), 1g grain sizes are the talcum powder of 50nm, then are added wherein 100mL toluene solvants add the neopelex of 23mg after being stirred by mixing under the conditions of 50 DEG C, The bentonite of 14mg is heated to 70 DEG C the reaction was continued 4h, product is placed in suitable mold dried in 50 DEG C of vacuum after completion of the reaction Drying for 24 hours, finally obtains a kind of dynamic aggregation object in case.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, Using cupping machine carry out extension test, rate of extension 10mm/min, measure sample tensile strength be 12.34 ± 0.98MPa, elongation at break are 55 ± 9%.There are four the stage, hydrogen bond-has product stress-strain diagram in present embodiment Machine boric acid estersil key-organic boronic acid anhydride key-organic boronic cyclic ester key stepwise dissociation successively realizes the dissipation step by step to energy, Improve the performance of the intensity and good dynamic of material.After the polymer samples broken are recycled, applies good pressure and be placed in 2-3h is placed in heating in 80 DEG C of vacuum drying oven, and section can be bonded voluntarily, is molded again, and properties of sample after molding reaches as former state The 95% of product.In the present embodiment, the functional characteristic embodied using polymer samples can be filled in as a kind of sealing It exercises and uses.

Embodiment 14

Take 54g boric acid ester copolymer (using AIBN as initiator, by 1- allyl -2,4- dioxos -1,2,3,4- tetrahydrochysenes - 5- pyrimidines nitrile and propylene ylboronic acid diisopropyl ester are made by free radical polymerization), 23g sodium alginates, 4g diphenyl silanes, 3g 4- hydroxylphenylethyl alcohols, 70g o-phthalic acid dibutyl esters, 8g MBS toughener, 2g stearic acid, 0.5g irgasfos 168s, 0.4g antioxygens Agent 1010,0.3g tin dilaurates dioctyl tin, 1g dimethicones after mixing, are warming up to 80 DEG C, are stirred to react 2h, then It takes out, is placed in mold, 6h is placed under the conditions of 50 DEG C of nitrogen protections and carries out subsequent reactions, finally obtains plasticizer swell gel Dynamic aggregation object.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, stretching survey is carried out using cupping machine Examination, rate of extension 10mm/min, it is 13.24 ± 0.79MPa to measure sample tensile strength, and elongation at break is 84 ± 8%, this There are four stage, hydrogen bonds-organic boronic estersil key-organic boronic cyclic ester key-for product stress-strain diagram in embodiment Organic boronic monoester bond stepwise dissociation successively realizes the dissipation step by step to energy, improves the intensity of material and good dynamic Performance.In addition, after the polymer samples broken are recycled, applies good pressure and be placed in heating placement in 60 DEG C of vacuum drying oven 1-3h, section can be bonded voluntarily, be molded again, and properties of sample after molding reaches the 93% of raw sample.In the present embodiment, may be used Gel tubing is made in polymer samples to use, after its appearance is damaged, it can be recycled and reused.

Embodiment 15

55g borate ester Grafted Polyethylenes alcohol is taken (using polyvinyl alcohol as raw material, it to be reacted to obtain side with acryloyl chloride Chain contains the copolymer of double bond, then it is made final with 2- mercaptophenyl boronic acids pinacol ester by thiol-ene click-reactions Product), acrylamide-boric acid copolymer of 13g (reacts as raw material using 1- amino-ethyl boric acid diisopropyl ester, acryloyl chloride and made Obtain borate acrylamide monomer 1；It is reacted as raw material using isocyanates ethyl acrylate, ethamine and monomer 2 is made；By monomer 1, list Body 2 and N, N- dimethacrylamide obtain final product by free radical polymerization), 17g oxazolidones-catechol copolymer (by allyl hydroxyethyl ether and 5- chloromethyl -2- oxazolidones in molar ratio 1:1 is dissolved in toluene, using potassium carbonate as catalyst, with Tetrabutylammonium bromide is that Xi Bing oxazolidinones are made in consisting of phase-transferring agent reaction, by itself and n-isopropyl acrylamide, catechol Under the action of benzoyl peroxide (BPO) carry out free radical polymerization and be made), 5g isoliquiritigenins, 10g AC foaming agents, 2g oxygen Change zinc, 8g calcium carbonate, 0.5g stearic acid, 0.2g irgasfos 168s, 0.3g antioxidant 1010s, 0.5g di-n-butyltin dilaurates After mixing, it is added in small-sized internal mixer progress mixing blending, wherein blending temperature is 100 DEG C, is blended the time and is After mixing, sample is taken out, is put into twin-roll machine and suppresses flakiness, is cooled down at room temperature by 10min, and cut-parts will make The polymer flake obtained, which is dipped in 90 DEG C of water, carries out precrosslink, then takes out, and 6h is placed in 80 DEG C of vacuum drying ovens into traveling The reaction and drying of one step, are cooled to are placed at room temperature for 30min later.It is removed from the molds mixing print, is taken after being shredded suitable Amount is placed in suitable mold, and vulcanizing press is utilized to carry out foaming, wherein molding temperature is 130-140 DEG C, when molding Between be 20-30min, pressure 10MPa, soft foam of polymers sample is finally obtained, with good pliability, and can It is stretched on a large scale.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, is carried out using cupping machine Extension test, rate of extension 10mm/min, measure sample tensile strength be 14.76 ± 0.45MPa, elongation at break be 27 ± 2%.After polymer material is cut off, placing it in application pressure in 100 DEG C of mold can be molded again, sample after molding Performance reaches the 90% of raw sample, and the self-healing properties having using it can be reused.It in the present embodiment, can be by this Dynamic aggregation object material is used for making recuperability bubble wrap material.

Embodiment 16

25g organoboron compounds are taken (to react and make as raw material using 4- hydroxy benzenes pinacol borate, hexamethylene diisocyanate ) be added in the reaction bulb of dried and clean, 200mL THF solvents are added, is heated to 60 DEG C and is stirred dissolving, be then added dropwise Enter 20% a small amount of acetic acid aqueous solution, then weigh 4.32g diphenyl silanodiols and be added in mixed solution, is subsequently added into 2.6g Sample after the reaction was continued 4h, is placed in 50 DEG C by 1,1'- (1,3- phenylene) bis- (ethane -1,2- glycol) and 2.5g daizeols It is dried in baking oven and removes solvent for 24 hours, be cooled to be placed at room temperature for 30min later, sample is shredded, take 25g samples, 25g phenyl boric acids Modification by copolymerization isoprene rubber (using AIBN as initiator, isoprene, n-isopropyl acrylamide and 3- vinylphenylboronic acids is led to Cross free-radical polymerized obtain) be added to and carry out mixing 20min in small-sized internal mixer after, 7g white carbons, 8g titanium dioxides, 0.1g is added Barium stearate, 0.3g stearic acid continue to be kneaded 20min.After additive is sufficiently mixed uniformly with sizing material, the material after being kneaded is taken out It is cooled down, is placed in twin-roll machine and suppresses flakiness, cooled down at room temperature, cut-parts.Polymer flake obtained is dipped in It is crosslinked, is then taken out in 90 DEG C of water, 6h is placed in 80 DEG C of vacuum drying ovens and is further reacted and is dried, later It is cooled to and is placed at room temperature for 30min, be removed from the molds sample, the dynamic aggregation object material of rubbery state is finally obtained, with good Good plasticity, can be prepared into product of different shapes, and stretching extension can be carried out in wide range, body according to die size Reveal very excellent tensile toughness.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, utilizes tension test Machine carries out extension test, and rate of extension 10mm/min, it is 8.13 ± 0.87MPa, elongation at break to measure sample tensile strength It is 55 ± 5%, the organic boric acid ester dynamic key of four types, side hydrogen bond, skeleton hydrogen bond dissipate according to its dynamic stepwise dissociation Energy greatly increases the intensity of material.After surface of polymer material is delineated with blade, 80 DEG C of vacuum are placed it in After placing 2h in baking oven, cut disappears and (may be selected to surface slightly soak during this), and sample can carry out selfreparing. This polymer material can be made into instrument transport protection shell and be used.

Embodiment 17

The boric acid modified silicon rubber of 25g is weighed (with methyl vinyl silicone rubber, 4- sulfydryl fourths boric acid (by 4- bromo fourth boric acid It is added dropwise in the thiocarbamide ethanol solution of heat, is being heated to reflux together with potassium hydroxide aqueous solution, is obtaining product) it is raw material, with DMPA is as photoinitiator, under the conditions of ultraviolet light, is made by mercaptan-alkene hydrocarbon click addition reactions), 15g silanols change Property silicon rubber is (using methyl vinyl silicone rubber, γ-mercapto hydroxypropyl methyl dimethoxysilane as raw material, using DMPA as light-initiated Agent after intermediate product is made by mercaptan-alkene hydrocarbon click addition reactions, then hydrolyzes to obtain final under the conditions of ultraviolet light Product), 13g dihydroxy primitives modified silicon rubber is (using methyl vinyl silicone rubber, 3- sulfydryls -1,2-PD as raw material, three Under ethamine catalytic condition, by mercaptan-alkene hydrocarbon click addition reactions be made), 6g carbon blacks, 1000 mesh of 3g conductive black, 2.7g di-iron trioxides, 0.3g silicone oil are added in small-sized internal mixer and are kneaded 40min, and additive is made to be sufficiently mixed uniformly with sizing material Afterwards, sizing material is taken out, 1h is heat-treated under the conditions of 120 DEG C.Sizing material is taken out later, is placed in suitable mold, in 80 DEG C of vacuum 4h is placed in baking oven, then in 10MPa forming under the pressure, obtains the dynamic aggregation object material of silicon rubber base.It is made using mold The dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes carries out extension test, rate of extension 10mm/ using cupping machine Min, it is 6.35 ± 0.68MPa to measure sample tensile strength, and elongation at break is 1224 ± 121%.Polymer material has good Good intensity and toughness, measuring its conductivity can change according to the stretching or compressive state of material, illustrate that material has Stress response；After polymer material is cut off, placing it in application pressure in 100 DEG C of mold can be molded again, be molded Properties of sample afterwards reaches the 93% of raw sample, which can be stretched in wide range, can be poly- by what is obtained Close object material be fabricated to antistatic sealing ring, high intensity stress sensing material or Embedding Material.

Embodiment 18

It weighs 25g borates modified polystyrene and (using AIBN as initiator, utilizes styrene and 4- vinylphenylboronic acids third Diol ester passes through free-radical polymerized be made), 21g it is poly- to phenylethyl alcohol, the silane-modified styrene-maleic anhydride copolymers of 18g (with P-methyl benzenesulfonic acid is catalyst, and 3- aminopropyltriethoxy dimethoxysilanes are reacted with styrene-maleic anhydride copolymer, will be produced Obtained after object hydrolysis), 12g AC foaming agents, 5g zinc oxide, 7g calcium carbonate, 0.5g stearic acid, 0.2g irgasfos 168s, 0.3g it is anti- Oxygen agent 1010,0.5g di-n-butyltin dilaurates after mixing, are added to progress mixing blending in small-sized internal mixer, In, blending temperature be 100 DEG C, the blendings time be 30min, after mixing, sample is taken out, be put into twin-roll machine be pressed into it is thin Piece is cooled down at room temperature, and polymer flake obtained is dipped in 90 DEG C of water and carries out precrosslink by cut-parts, then takes out, 6h is placed in 80 DEG C of vacuum drying ovens further to be reacted and dried, and is cooled to is placed at room temperature for 30min later.From mold It takes out and is kneaded print, take and be placed in right amount in suitable mold after being shredded, foaming is carried out using vulcanizing press, In, molding temperature is 130-140 DEG C, clamp time 10-15min, pressure 10MPa and finally obtains the polymer of semi-rigid Foam sample with good pliability, and can be stretched on a large scale.It is made into 80.0 × 10.0 × 2.0mm rulers Very little dumbbell shape batten carries out extension test using cupping machine, and rate of extension 10mm/min measures sample tensile strength For 8.25 ± 0.56MPa, elongation at break is 25 ± 2%.After polymer material is cut off, polymer material is cut off it Afterwards, placing it in application pressure in 60 DEG C of mold can be molded again, and properties of sample after molding reaches the 92% of raw sample, profit The self-healing properties having with it can be reused.In the present embodiment, having using material obtained can selfreparing Characteristic, can use it for make wall protective materials used.

Embodiment 19

The organoboron compound of 5.6g is added in No. 1 reactor (by propylene ylboronic acid diisopropyl ester and 1,3,5- triazines- For 2,4,6- tri- mercaptan using AIBN as initiator, triethylamine is catalyst, by thiol-ene click-reactions be made), 4.1g boric acid The four arm compounds (a) (being made by hydrocarbyl reaction with tetrabromo season amylalcohol using 2- aminomethyl phenyls boric acid) of sealing end, 0.7g stones Black alkene, 100mL DMF solvents are heated to 80 DEG C and are stirred dissolving after ultrasonic echography disperses 40min, then are added dropwise to few 20% acetic acid aqueous solution of amount, continues after being stirred 30min, is slow added into the hydroxy-end capped methyl phenyl silicone oils of 12.5mL (molecular weight is about 12,000) after being stirred 30min, is added 2mL triethylamines, continues to be stirred to react 3h under the conditions of 80 DEG C, Polymer is placed in 80 DEG C of vacuum drying ovens to dry and removes solvent for 24 hours, is cooled to is placed at room temperature for 30min later.It is made into again The dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes carries out extension test, rate of extension 10mm/ using cupping machine Min, it is 8.34 ± 1.46MPa to measure sample tensile strength, and elongation is 51 ± 5%, can be as a kind of anlistatig anti- Shield shell is used；After polymer material is cut off, placing it in 60 DEG C of mold can be again after applying pressure 1-2h Molding, properties of sample after molding reach the 95% of raw sample.

Embodiment 20

The three arm polysiloxanes that 27g boric acid blocks are added in No. 1 reactor (is with 3- bromo- 4- (bromomethyl) benzaldehyde It is reacted for 24 hours with methyltriphenylphospbromide bromide phosphorus, potassium tert-butoxide, then is warming up to 100 DEG C in water/dioxy six by raw material at room temperature Ring in the mixed solvent is reacted for 24 hours, then it is reacted in DMF solvent with tert-butyl chloro-silicane, imidazoles to 20h, then by its 4h is reacted in tetrahydrofuran solvent with methanol, methoxyl methyl chlorine, then using Mg as catalyst, be heated to 60 DEG C of reaction 3h, then Butyl borate is added and reacts at room temperature 8h, 2- (methylol) phenyl boric acid ring-type monoesters ethylene is obtained after purification；With prestox ring four Siloxanes, phenyl three (dimethyl siloxane) silane are raw material, and the concentrated sulfuric acid is catalyst, and three ends are synthesized by ring-opening polymerisation method Hydrogen-based polysiloxanes, then it is anti-by Si―H addition reaction under Pt catalytic conditions with 2- (methylol) phenyl boric acid ring-type monoesters ethylene Should be made) and 200mL THF solvents, after being heated to 60 DEG C of stirring and dissolvings, then 3.02g ellagic acids, 3.6g are added into reactor 4,4'- xenols, 5.4g 4, bis- (Isosorbide-5-Nitrae-benzene) hypoboric acid of 4'- oxos, after being stirred 30min, are added the triethylamine of 2.5mL, It is reacted under the conditions of 80 DEG C, in reaction process, solution viscosity constantly rises, and after heating reaction 4h, dynamic aggregation object is made Solution, the solution can with after other mixed with polymers, by evaporation of the solvent it is complete after, other common polymer are modified, So that it is obtained dynamic property, can be used as a kind of modifying agent.

Embodiment 21

A certain amount of modified polynorbornene is taken (using vinyl boron bromine alkane, cyclopentadiene as raw material, to pass through Diels-Alder Boric acid modified norbornene is made in reaction；After vinylamine is reacted with carbethoxyl group isocyanates, then pass through with cyclopentadiene The norbornene of amoyl modified is made in Diels-Alder reactions；Norbornene, the drop of amoyl modified that boron bromine alkane is modified Bornylene, using metallocene catalyst/methylaluminoxane as catalyst system and catalyzing, is made final with norbornene by polyaddition reaction Product) solution that 0.1mol/L is configured in o-dichlorohenzene solvent is dissolved by heating, therefrom take 60mL to be added to No. 1 reactor In, it is added dropwise to a small amount of deionized water and acetic acid stirs evenly for use.The polyethylene of 8.3g is slowly added into No. 1 reactor The 1 of alcohol, 1.45g, 1,3,3,5,5- hydroxyl -1,3, tri- silicon of 5- raise the temperature to 80 DEG C, are stirred to react 30min for hexamethylene, Then 2mL triethylamines are added, then reaction solution is poured into suitable mold, is placed in 60 by the reaction was continued under the conditions of 80 DEG C 4h It is further reacted and is dried for 24 hours in DEG C vacuum drying oven, be cooled to be placed at room temperature for 30min later, finally obtain gelatinous Polymer material, sample have good elasticity and toughness, can extend in wide range.It is made into 80.0 × 10.0 The dumbbell shape batten of × 2.0mm sizes carries out extension test using cupping machine, and rate of extension 10mm/min measures sample Product tensile strength is 4.67 ± 0.58MPa, and elongation at break is 538 ± 86%, organic boronic estersil key, organic boronic cyclic ester key With the stepwise dissociation of hydrogen bond, the performance of material dissipation energy step by step is realized, higher intensity and elongation are made it have.It will gather After closing the cut-out of object material, place it in 60 DEG C of mold after applying pressure 1-2h to be molded again, sample after molding The 91% of raw sample can be reached.In addition, product obtained also has good plasticity, it can be positioned over difference according to actual needs In the mold of shape, and slightly apply certain stress under the conditions of certain temperature, you can be shaped to according to mold of different shapes Polymeric articles.In the present embodiment, polymer can be made to resilience washer and shock resistance gasket uses.

Embodiment 22

32g acrylate copolymers are added in three-necked flask (by 1- amino-ethyls pinacol borate and acryloyl chloride Borate acrylate monomer 1 is made in reaction；Isocyanates ethyl acrylate is reacted with ethamine, the acrylic acid containing urea bond is made Ester monomer 2, then using AIBN as initiator, itself and borate acrylate monomer 1, methyl acrylate are obtained by emulsion polymerization To), 100mL acetone solvents, be heated to 50 DEG C be stirred dissolving after, add the deionized water of 10mL, be added dropwise to a little second Acid is then slowly added into 21g Silane Grafteds modified polyvinylalcohol and (using polyvinyl alcohol as raw material, it is reacted with acryloyl chloride Side chain contains the copolymer of double bond, then by it with thiopurine methyltransferase methyldiethoxysilane by thiol-ene click-reactions, will produce Object hydrolysis is made), 2g carbon fibers and 3.6g 3- (methylol) -1- adamantanols, after being stirred dispersion 6h, in 80 DEG C of conditions Under continue to be stirred reaction 3h.Solvent is sloughed by decompression suction filtration and obtains residue, and dynamic aggregation object is obtained after being purified Solid, the product have good intensity and toughness simultaneously.After polymer material is crushed, place it in 60 DEG C of mold It can be molded again after applying pressure 1-2h, properties of sample after molding reaches the 90% of raw sample.It can be made into certainly The penholder or pen container for repairing characteristic use.

Embodiment 23

7g organoboron compounds (react and be made as raw material using 4- hydroxyl fourth boric acid magnesium salts, the pungent diisocyanate of 1,8-) are taken to add Enter into No. 1 reactor, 200mL THF solvents are added, is heated to 60 DEG C and is stirred dissolving, be then added dropwise to a small amount of 20% Acetic acid aqueous solution is heated to 60 DEG C, and 10g vinyl pyrrolidones-silane copolymer is slowly added under stirring (with 2- third Olefin(e) acid -3- (diethoxymethylsilane base) propyl diester is raw material, and AIBN is initiator, itself and vinyl pyrrolidone are passed through Free radical polymerization, then product is hydrolyzed and is made) and the boric acid modified polynorbornenes of 5g (be former with vinyl boronic acids, cyclopentadiene Boric acid modified norbornene is made by Diels-Alder reactions in material；By boric acid modified norbornene and norbornene with Metallocene catalyst/methylaluminoxane is catalyst system and catalyzing, is made by polyaddition reaction), it is added dropwise to a small amount of triethylamine, is placed in Heating reaction 2h is carried out in 60 DEG C of water-baths.Sticky polymer solution is poured into suitable mold, 80 DEG C of vacuum is placed in and dries It is dry in case to be cooled to later for 24 hours and be placed at room temperature for 30min, gelatinous polymer material is finally obtained, sample has good bullet Property and toughness, can extend in wide range.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, profit Extension test is carried out with cupping machine, rate of extension 10mm/min, it is 0.86 ± 0.15MPa to measure sample tensile strength, Elongation at break be 685 ± 77%, organic boronic estersil key, organic boronic acid anhydride key and hydrogen bond stepwise dissociation, realize material The performance of dissipation energy step by step makes it have higher intensity and elongation.After polymer material is cut off, 60 are placed it in DEG C mold in apply pressure 1-1.5h after can be molded again, properties of sample after molding reaches the 95% of raw sample.In addition, system The product obtained also has good plasticity, can according to actual needs be positioned in mold of different shapes, and in certain temperature Under the conditions of slightly apply certain stress, you can polymeric articles of different shapes are shaped to according to mold.It can be by dynamic aggregation object It is used as bulletproof glass squeegee as with selfreparing.

Embodiment 24

Be added in No. 1 reactor 24g borates-ethylene copolymer (using AIBN as initiator, will be different under the conditions of 80 DEG C Propylene ylboronic acid pinacol ester and ethylene carry out random copolymerization and are made), 4g sorbierites, the pungent hypoboric acid of 7.5g 1,8-, 3g be modified it is poly- Ethylene glycol, 1.5g Graphene powders, 0.3g neopelexes add 0.2g's after stirring 30min under the conditions of 60 DEG C Bentonite is heated to 80 DEG C and is stirred hybrid reaction, and after hybrid reaction 3h, sticky polymer solution is poured into suitable mold In, be placed in 80 DEG C of vacuum drying ovens it is dry be cooled to later for 24 hours and be placed at room temperature for 30min, finally obtain be dispersed with graphene from Sub- liquid gel polymer samples, after being pressed sample surfaces with finger, sample can show good elasticity, and can Stretching extension is carried out in wide range.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm sizes, is tried using stretching It tests machine and carries out extension test, rate of extension 50mm/min, it is 5.23 ± 0.45MPa, extension at break to measure sample tensile strength Rate is 343 ± 72%.Polymer samples in the present embodiment have embodied good self-repairability, are cut with a knife and break it Afterwards, section part is slightly applied to pressure to be bonded and (may be selected that section slightly soak during this), 60 DEG C of moulds are placed in Section can bond again after heating 90min in tool.Dynamic aggregation object sample in the present embodiment, can be as a kind of graphene Composite intelligent Heat Conduction Material is used, the strong thermal conductivity based on graphene, is conducive to carry out internal minor damage in heating shape Quick reparation under state.Further, since the high conductivity of graphene, makes the dynamic aggregation object in the present embodiment in different stress There is different conductivity, the material can be used as strain gauge under state.

Embodiment 25

Take a certain amount of polyol compound (c) (using tetraallyloxyethane, 3- sulfydryls -1,2-PD as raw material, methanol For solvent, triethylamine is catalyst, is made by mercaptan-alkene hydrocarbon click addition reactions) it is dissolved in methanol solvate, it is configured to The solution of 0.2mol/L；14g organoboron compounds (a) are added in No. 1 reactor [by carbamate compounds (with different Ethyl cyanate, propylene glycol mono allyl ether are that raw material reaction is made) lead under the action of AIBN with allyl pinacol borate Free radical polymerization is crossed to be made], 100mL methanol solvates, the methanol solution of 30mL polyol compounds (c), 10g hydrogenation terminal hydroxy groups it is poly- Butadiene (hydrogenation HTPB, Mn=3000) (d), 7g silane compounds (b) are (with dicyclohexylcarbodiimide, 4- dimethylamino pyrroles Pyridine is catalyst, and carrying out condensation reaction using 3- aminopropyltriethoxies dimethoxysilane and adipic acid is made), 1mL triethylamines, stir After mixing uniformly, 3h is reacted under the conditions of 60 DEG C of nitrogen protections, 1.5g expended microsphere foaming agent ultrasonic mixing 1min is added, by it It is placed in suitable mold, continues reacting drying for 24 hours in 80 DEG C of vacuum drying ovens, be cooled to be placed at room temperature for 30min later, from mould Sample is taken out in tool, foaming is carried out using vulcanizing press, wherein molding temperature is 140-150 DEG C, and clamp time is 10-15min, pressure 5MPa finally obtain dual-network dynamic aggregation object foamed material.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm sizes carries out extension test using cupping machine, and rate of extension 50mm/min measures sample Tensile strength be 4.53 ± 0.46MPa, elongation at break be 683 ± 68%, organic boronic cyclic ester key, organic boronic monoester bond, The stepwise dissociation of organic boronic estersil key and hydrogen bond improves the ability of material dissipation energy, make its possess good intensity and Toughness.After polymer material is crushed, place it in 60 DEG C of mold after applying pressure 1-1.5h to be molded again, be molded Properties of sample afterwards reaches the 92% of raw sample.The dynamic aggregation object has good isolation vibrations and stress buffer effect, together When also maintain a degree of ductility, polymer material obtained can be applied to make household electrical appliances insulated product or automobile and hindered Buddhist nun's anti-vibration article.

Embodiment 26

A certain amount of dendritic organoboron compound (a) is taken (to draw using 2,2- dimethoxy-phenylfs ethyl ketone (DMPA) as light Agent is sent out, ultraviolet light is light source, and by vinyl boronic acids and 1, mercapto is made by mercaptan-alkene hydrocarbon click addition reactions in 2- dithioglycols Ylboronic acid；Using DMPA as photoinitiator, ultraviolet light is light source, and by triallylamine and 1,2- dithioglycols pass through mercaptan-alkene After level-one intermediate product is made in hydrocarbon click addition reactions, then with triallylamine to continue through mercaptan-alkene hydrocarbon click additions anti- Two level intermediate product should be made, be made among three-level by mercaptan-alkene hydrocarbon click addition reactions with 1,2- dithioglycols again later Product, then reacted with triallylamine and level Four intermediate product is made, finally pass through mercaptan-with sulfydryl boric acid, 1,2- dithioglycols Final product is made in alkene click addition reactions) it is dissolved in the solution that 0.01mol/L is configured in toluene solvant, 0.2mg is added BHT antioxidant；A certain amount of hydroxy-end capped dimethicone (b) heating for dissolving is taken to be configured in toluene solvant The solution of 0.2mol/L.30mL organoboron compounds solution and silicon oil solution, 1,8- ethohexadiols (c), 16g organic boronics is respectively taken to change (using methyl mercapto silicon rubber, vinyl boronic acids as raw material, DMPA is as photoinitiator, in ultraviolet light item for property silicon rubber (d) Under part, it is made by thiol-ene click-reactions) it is added in the reaction bulb of dried and clean, 1mL triethylamines are added, stirring is equal After even, 4h is reacted under the conditions of 60 DEG C of nitrogen protections, is placed it in suitable mold, the reaction was continued in 80 DEG C of vacuum drying ovens Drying for 24 hours, is cooled to is placed at room temperature for 30min later, be removed from the molds sample, be made into 80.0 × 10.0 × 2.0mm rulers Very little dumbbell shape batten carries out extension test using cupping machine, and rate of extension 50mm/min measures sample tensile strength For 5.13 ± 0.73MPa, elongation at break is 853 ± 167%.After polymer samples are broken, it is placed in 80 DEG C of mold After applying certain pressure fitting 1h (may be selected to section slightly soak during this), sample can be again adhesion-molded, The performance of sample reaches the 93% of raw sample after molding, has good dynamic and self-repairability.In actual use, It can be used as a kind of recuperability elastic string.

Embodiment 27

A certain amount of acrylamide-boric acid ester copolymer (a) is weighed (with 1- amino-ethyl boric acid diisopropyl ester, acryloyl Chlorine is that borate acrylamide monomer is made in raw material reaction, then it is obtained with N,N-DMAA by free radical polymerization To final product) it is dissolved in the solution that 0.4mol/L is configured in deionized water；It is above-mentioned molten that 40mL is added in No. 1 reactor Liquid, 100mL THF, 2.3g containing silicone hydroxyl/silicone hydroxyl presoma compound (b) (with 3- aminopropyltriethoxies dimethoxysilane, Adipoyl Chloride is that raw material reaction is made), after being stirred 30min, 2mL triethylamines and 8.5g acrylamides-boric acid copolymerization is added (using 3- bromopropyls boric acid, allylamine as raw material, (3- (allyl amino) propyl) boric acid is made by hydrocarbyl reaction in object (c) Afterwards, then by it with N,N-DMAA using AIBN as initiator, carry out free radical polymerization and obtain final product), and 2.72g pentaerythrites (e) continue to be stirred to react 2h under the conditions of 60 DEG C, 2.5g hollow glass microballoons, 3g bentonite, 0.5g are added Stearic acid and 0.5g oleic acid, heating stirring after mixing, are placed in 60 DEG C of baking ovens to place and are dried for 24 hours and further Reaction finally obtains the solid elastomer with certain elasticity and places it in 60 DEG C of mold after being crushed polymer material It can be molded again after middle application pressure 1-2h, properties of sample after molding reaches the 94% of raw sample.It can be using the material as one Kind lightweight flexible bead is used.

Embodiment 28

The organoboron compound (e) of a certain amount of dissaving structure is taken (using diethanol amine, methyl acrylate as raw material, to synthesize 3- (bis- (2- ethoxys) amino) methyl propionate；Again by it in the form of dropwise addition with trimethylolpropane in Catalyzed by p-Toluenesulfonic Acid Under the conditions of, reacted at 115 DEG C and level-one intermediate product be made, then again with 3- (bis- (2- ethoxys) amino) the methyl propionate system of reacting Two level intermediate product is obtained, after then being blocked using 3- isocyanide acid propylenes, then with 4- sulfydryl fourths boric acid (by 4- bromo fourth boric acid It is added dropwise in the thiocarbamide ethanol solution of heat, is being heated to reflux together with potassium hydroxide aqueous solution, is obtaining product) pass through thiol- Final product is made in ene click-reactions) it is dissolved in the solution that 0.2mol/L is configured in chloroform solvent；Take a certain amount of silicon Hydroxyl graft modification butyl rubber (b) (using brombutyl, thiopurine methyltransferase methyldiethoxysilane as raw material, is made with DMPA Product is made by mercaptan-alkene hydrocarbon click addition reactions, then product is hydrolyzed under the conditions of ultraviolet light for photoinitiator Obtain) it is dissolved in the solution that 0.2mol/L is configured in chloroform solvent；The organic boronic of 23g is added in No. 1 reactor Ester sealing end four arm ester type compounds (a) (by isopropenyl pinacol borate and four -3-thiopropionate of pentaerythrite with AIBN is initiator, triethylamine is catalyst, is made by thiol-ene click-reactions), 200mL chloroforms, 14g it is poly- Glycol copolymer (d) is (with ethylene glycol, ethylene oxide, 2- methyl-2-propyls [3- (2- Oxyranyles) propyl] carbamic acid Ester is raw material, and boron trifluoride ether is catalyst, is synthesized by cation ring-opening polymerization), 15g polyvinyl alcohol (c), 30mL it is organic The chloroform soln of boron compound (e), the chloroform soln of 30mL silicone hydroxyl graft modification butyl rubbers (b), at 80 DEG C Under the conditions of stir evenly after after reaction 30min, 2mL triethylamines, 0.2g titanium dioxide ground in advance, ultramarine, chrome yellow, phthalein is added Ultramarine, soft carbon mixed-powder, 0.3g organobentonites, 0.5g dimethyl silicone polymers, 0.4g hydroxyethyl celluloses, 0.2g Dibutyl tin laurate, particle fluorescence brightening agent KSN, 30mg light stabilizer 770,0.3g nano silicon dioxides, in 50 DEG C of items Continue to be stirred to react 4h under part, stop reaction, after being placed at room temperature for 12h, then the organic coating being made of dynamic aggregation object can be obtained Lotion after drying coating coated in surface of bottom material, then forms scratch-resistant, peelable regenerated coating.

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

1. a kind of dynamic aggregation object containing combination dynamic covalent bond, contains at least two class dynamic covalent bonds, wherein described Dynamic covalent bond is organic boronic ester bond.

2. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that the organic boron Acid esters key is at least selected from organic boronic cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key Combination.

3. the dynamic aggregation object according to claim 2 containing combination dynamic covalent bond, which is characterized in that described is organic Boric acid cyclic ester key, selected from such as lower structure：

Wherein, a boron atom forms cyclic annular organic boronic ester units with two oxygen atoms simultaneously；Boron atom in the structure 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；L is linker；

The organic boronic monoester bond, selected from such as lower structure：

Wherein, the oxygen atom being connected by the atom in addition to the boron atom with two when single one boron atom difference is formed Hexatomic ring or hexatomic ring cyclic annular organic boronic ester units below；In the structure at least one carbon atom by boron carbon key with Boron atom is connected；L₀、L₁、L₂、L₃、L₄For linker, L₀Skeletal atom there are two at least containing；

The organic boronic estersil key, selected from such as lower structure：

Wherein, a boric acid estersil key (B-O-Si) is at least formed between boron atom and silicon atom；At least one in the structure A carbon atom is connected by boron carbon key with boron atom, and at least one organic group is keyed to boron atom by the boron carbon On；

The organic boronic acid anhydride key, selected from such as lower structure：

Wherein, a boric acid acid anhydride key (B-O-B) is at least formed between boron atom and boron atom；Each boron atom is extremely in the structure It is few 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；L₃、L₄For linker.

4. the dynamic aggregation object according to claim 2 containing combination dynamic covalent bond, which is characterized in that described is organic Boric acid cyclic ester key, organic boronic monoester bond, organic boronic estersil key and organic boronic acid anhydride key by organic boronic primitive respectively with Dihydroxy primitive, single hydrocarbon hydroxyl primitive, silicone hydroxyl/silicone hydroxyl presoma, organic boronic elementary reaction are formed；Wherein, described Organic boronic primitive is at least selected from organic boron acidic group, organic boronic ester group, organic boronic alkali, organic boron alkylhalide group；Its In, the dihydroxy primitive is at least selected from 1,2- glycol primitive, 1,3- glycol primitive, adjacent two phenolic hydroxyl group primitives, 2- hydroxyl first Base phenolic hydroxyl group primitive；Wherein, single hydrocarbon hydroxyl primitive, be at least selected from single alkanol hydroxyl primitive, monoene alcoholic extract hydroxyl group primitive, Single phenol hydroxyl primitive, the polyphenol hydroxyl primitive in meta position, between polyphenol hydroxyl primitive and adjacent hydroxyl groups in contraposition between Every the polyhydroxy primitive of at least four atoms；Wherein, the silicone hydroxyl, refer to by silicon atom and with the silicon atom phase The structural motif that a hydroxyl even is formed；Wherein, the silicone hydroxyl precursor, refer to by silicon atom and with this A connected hydrolyzable of silicon atom obtains the structural motif that the group of hydroxyl is formed.

5. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that the dynamic Also contain supermolecule hydrogen bond action in polymer or its composition.

6. the dynamic aggregation object according to claim 5 containing combination dynamic covalent bond, which is characterized in that described in being formed The hydrogen bond group of supermolecule hydrogen bond action contains following constituent：

7. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that the dynamic Polymer has non-crosslinking structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, all types of dynamics are covalent The sum of degree of cross linking of key is less than gel point.

8. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that the dynamic Polymer has non-crosslinking structure, contains at least two class dynamic covalent bonds and hydrogen bond；Wherein, all types of dynamic covalent bonds The degree of cross linking in its gel point hereinafter, the degree of cross linking of supermolecule hydrogen bond in gel point hereinafter, and dynamic covalent bond and hydrogen bond The sum of degree of cross linking is less than gel point.

9. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that the dynamic Polymer has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein all types of dynamics are total The degree of cross linking of valence link is more than gel point.

10. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein at least a kind of dynamic is altogether The degree of cross linking of valence link is more than gel point, and the degree of cross linking of at least a kind of dynamic covalent bond is below gel point.

11. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds but does not contain hydrogen bond, wherein all types of dynamics The degree of cross linking of covalent bond in gel point hereinafter, but the sum of its degree of cross linking more than gel point.

12. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamic covalent bonds The degree of cross linking more than its gel point, the degree of cross linking of hydrogen bond is more than gel point.

13. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamic covalent bonds The degree of cross linking more than its gel point, the degree of cross linking of hydrogen bond is below gel point.

14. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein at least a kind of dynamic covalent bond The degree of cross linking is more than gel point, and the degree of cross linking of at least a kind of dynamic covalent bond is in gel point hereinafter, the degree of cross linking of hydrogen bond is in gel Or more.

15. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamic covalent bonds The degree of cross linking in its gel point hereinafter, the degree of cross linking of hydrogen bond is more than gel point.

16. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein all types of dynamic covalent bonds The degree of cross linking in its gel point hereinafter, the degree of cross linking of hydrogen bond in gel point hereinafter, but dynamic covalent bond and hydrogen bond the degree of cross linking The sum of be not less than gel point.

17. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that described is dynamic State polymer has cross-linked structure, contains at least two class dynamic covalent bonds and hydrogen bond, wherein at least a kind of dynamic covalent bond The degree of cross linking is more than gel point, and the degree of cross linking of at least a kind of dynamic covalent bond is in gel point hereinafter, the degree of cross linking of hydrogen bond is in gel Or less.

18. the dynamic aggregation object according to claim 1 containing combination dynamic covalent bond, which is characterized in that constitute dynamic The recipe ingredient of polymer further include it is following any or appoint it is several can additive：Other polymers, auxiliary agent, filler；

Wherein, addible other polymers are selected from following any or appoint several：Natural polymer, synthetic resin, Synthetic rubber, synthetic fibers；

Wherein, addible auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, chain extender, toughener, coupling agent, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, Emulsifier, dispersant, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent；

Wherein, addible filler is selected from following any or appoints several：Inorganic non-metallic filler, metal packing, organic filler.

19. the dynamic aggregation object containing combination dynamic covalent bond according to any one of claim 1 to 18, feature exist In the form of the dynamic aggregation object or its composition is with following any：Solution, cream, glue, gel, is commonly consolidated lotion Body, elastomer, foamed material.

20. the dynamic aggregation object containing combination dynamic covalent bond according to any one of claim 1 to 18, feature exist In the dynamic aggregation object or its composition are applied to following product：Damper, padded coaming, energy-absorbing material, defense of resistance to impact Material, athletic protective article, army and police's protective article, force snesor, self-repairability coating, sound insulation deadener, self-repairability plate Material, self-repairability binder, bulletproof glass squeegee, toughness material, shape-memory material, sealing element, toy.

21. a kind of method of energy-absorbing, which is characterized in that provide a kind of dynamic aggregation object or its group containing combination dynamic covalent bond Energy-absorbing is carried out as energy-absorbing material at and using it, contains at least two class dynamic covalent bonds in the dynamic aggregation object, wherein institute The dynamic covalent bond stated is organic boronic ester bond, is at least selected from organic boronic cyclic ester key, organic boronic monoester bond, organic boronic The combination of estersil key and organic boronic acid anhydride key.