CN108341962A

CN108341962A - A kind of dynamic aggregation object and its application

Info

Publication number: CN108341962A
Application number: CN201710056036.5A
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

Abstract

The invention discloses a kind of dynamic aggregation object, contain the organic boronic ester bond and optional supermolecule hydrogen bond by organic boronic primitive and the generation of monohydroxy elementary reaction；Wherein, the organic boronic ester 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.Due to organic boronic ester bond and the dynamic reversibility of optional supermolecule hydrogen bond so that the polymer material has selfreparing, reusability and recuperability；In addition, the polymer material of special formulation, when by outer force effect, based on the dynamic of dynamic organic boronic ester bond, the dynamic aggregation object has energy dissipation and energy absorption characteristics, shows the functions such as good damping, damping, sound insulation, shock resistance, high tenacity.The dynamic aggregation object or its composition can be widely applied as anti-impact vibration-absorptive material, self-repair material, toughness material, force snesor, sealing material, squeegee etc..

Description

A kind of dynamic aggregation object and its application

Technical field

The present invention relates to intelligent polymer fields, and in particular to a kind of dynamic aggregation object and its application.

Background technology

Three big pillars (material, information, the energy) one of of the material as our times new technology revolution, with information technology, Energy technology together forms one of most important and most potential three big field in the 21 century world.New material is high in development It plays an important role in terms of new technology, transformation and promotion conventional industries, enhancing overall national strength and military capability of the country, and in nature Develop in science and field of engineering technology and is also getting faster.In recent years, various multifunction based on dynamic chemical, Intelligentized material is developed, and the development of new material is greatly facilitated in this.

Dynamic covalent chemical that dynamic chemical is combined in supramolecular chemistry and covalent chemical and the intersection to grow up Subject.In dynamic chemical field, " dynamic " is the concept of its core and essence.Supramolecular chemistry is to be based on non-covalent intermolecular Key interaction is formed by aggregation chemistry.Supermolecule has the characteristic of reversible " fracture " and " formation ", but these are non-total Valence interacts compared with traditional covalent bond, and bond energy is weaker, larger by thermodynamic effects, is formed by supramolecular structure at certain It is not the system of a dynamic stabilization in degree.Dynamic covalent chemical is similar with supramolecular chemistry, has suitable Under the conditions of reversible covalent bonds " fracture " and " formation " characteristic, and compared to supramolecular chemistry, the dynamic in dynamic covalent chemical The bond energy of covalent bond is or even close with non-dynamic covalent bond commonly greater than supermolecular mechanism power, this makes dynamic covalent bond comprehensive The invertibity of non-covalent bond and the firm sexual clorminance of common covalent bond are closed so that it is constructed in functional high molecule material, reviews one's lessons by oneself Answer and recycle recyclable etc. acquirement extensive use.

However, traditional dynamic covalent polymer is since the dynamic covalent bond dynamic that it contains is poor, dynamic aggregation object It obtains good dynamic to need to add catalyst or extraneous offer energy to accelerate equilibrium process, in addition certain dynamics are covalent There is certain defects in actual use for key itself, these all make the use environment and application field of dynamic aggregation object At limitation.For example, the reversible exchange reaction that traditional ester exchange reaction is people to be applied earliest, but the item of ester exchange reaction Part is harsher, and generally requiring could complete in the case where adding alkali, counterflow condition, while the dynamic activity of traditional ester bond is poor, from And limitation is produced to the application for the dynamic aggregation object constructed using ester exchange reaction；The imine linkage that primary amine is generated with aldehyde reaction, It is influenced strongly, to cause such imine linkage that must use within the scope of specific pH by acid-base value；Dynamic based on alcoxyl nitrogen base Reversible key, dissociation reaction temperature often will also reach 100-130 DEG C, meanwhile, the carbon center that the dissociation of alcoxyl nitrogen base generates is free To oxygen and high temperature sensitive, the irreversible bonding thus brought can impact the performance of material base；Contain three thioester groups Dynamic aggregation object then need could to occur under ultraviolet light or heating condition dynamic exchange reaction；In dynamic covalent bond Cystine linkage dynamic is preferable, can swap reaction under cryogenic, but mercaptan self stability is poor, use process Middle can be acted on surrounding air generates continuous oxidation and the mercaptans content in reversible system is constantly reduced, and influences making for material With.The presence of such situation so that characteristic possessed by dynamic covalent bond itself is difficult to obtain fully at typical condition Ground embodies, and needs to develop a kind of novel dynamic aggregation object, to solve the above-mentioned problems in the prior art.

Invention content

The present invention is directed to above-mentioned background, provides a kind of containing by organic boronic primitive and the generation of monohydroxy elementary reaction The dynamic aggregation object of organic boronic ester bond and optional supermolecule hydrogen bond.The dynamic aggregation object stability is good, general Temperate condition under can have good dynamic reversibility, and reflect self-repairability, reusability, recuperability And bionical mechanical property.

The present invention is achieved by following technical solution：

The present invention relates to a kind of dynamic aggregation objects, which is characterized in that it contains organic boronic primitive and monohydroxy primitive is anti- The organic boronic ester bond and optional supermolecule hydrogen bond action that should be generated；Wherein, the organic boronic ester bond is as dynamic The polymerization linking point of polymer and/or crosslinking linking point and exist, be the necessary condition to form or maintain dynamic aggregation object structure； And the dynamic aggregation object at least contains 3 organic boronic ester bonds as chain backbone group on any one chain direction；

The dynamic aggregation object, the polymer chain topological structure in forming are selected from line style, ring-type, branched, cluster, friendship Connection and combinations thereof form.

In the present invention, the organic boronic ester bond, at least one of structure as follows：

Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；Indicate with hydrogen atom, polymer chain, be crosslinked link or other The connection of any appropriate group, boron atom and carbon atom are accessed by least one connection in polymer chain respectively, Middle any two or two or moreBridge can be connected into；Wherein structural formula (2) or structural formula (3) if in two carbon atoms it is logical Cross two or moreCirclewise organic boric acid ester structure is connected, then it is heteroatomic hexatomic ring for the 6th atom Or it is arbitrary seven yuan and its above ring；Once B-O-C keys dissociate, the group or segment being preferably connected with C atoms just with B atoms Dissociation, being so conducive to the dynamic aggregation object has better dynamic.

In embodiments of the present invention, the dynamic organic boronic ester bond is by organic boronic primitive and monohydroxy primitive It reacts, wherein the organic boronic primitive is selected from but is not limited only to organic boron acidic group, organic boronic ester group, organic halogenation Boryl, organic boronic alkali and combinations thereof；It is preferred that using organic boron acidic group and monohydroxy primitive, organic boronic ester group and monohydroxy Primitive forms organic boric acid ester key, more preferably forms organic boric acid ester key using organic boron acidic group and monohydroxy primitive.

Heretofore described organic boron acidic group refers to a hydroxyl being connected by boron atom and with the boron atom The structural motif (B-OH) formed, 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 the present invention, a hydroxyl in organic boron acidic group (- OH) it is a functional group.

The organic boronic ester group, refer to by boron atom, an oxygen atom being connected with the boron atom and with the oxygen Structural motif that the connected alkyl of atom or silylation are formed (B-OR, wherein R be alkyl based on carbon, hydrogen atom or with Silylation based on silicon, hydrogen atom, is connected by carbon atom or silicon atom with oxygen atom), and boron atom therein at least with One carbon atom is connected by boron carbon key, and at least one organic group is keyed to by the boron carbon in boron atom. In the present invention, an ester group (- OR) in organic boronic ester group is a functional group.

The organic halogenation boryl, refer to by boron atom, a halogen atom being connected with the boron atom (F, Cl, Br, I) structural motif (B-F, B-Cl, B-Br, B-I) that 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 the present invention, organic halogenation A halogen atom (- F ,-Cl ,-Br ,-I) in boryl is a functional group.

The organic boronic alkali refers to being made of boron atom, a negative oxygen ion being connected with the boron atom Structural motif (B-O-) and include at least a cation (Mⁿ⁺, it is monovalence, divalent or Tricationic, is selected from but not It is only limitted to Li⁺、Na⁺、K⁺、Ni⁺、Ag⁺、NH₄ ⁺、Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺、Fe²⁺、Cu²⁺、Mn²⁺、Al³⁺、Fe³⁺), and it is therein Boron atom 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 the present invention, a negative oxygen ion (- O-) in organic boronic alkali is a functional group.

The monohydroxy primitive in the present invention, refers to by carbon atom and the hydroxyl being connected with carbon atom institute group At structural motif (C-OH), the dynamic organic boronic ester bond can be generated with organic boronic elementary reaction.It needs to refer to Go out, the hydroxyl in monohydroxy primitive of the present invention with organic boronic elementary reaction in addition to that can generate dynamic organic boronic Outside ester bond, it can also participate in reacting with other reactive groups.Dynamic organic boronic ester bond is generated with organic boronic elementary reaction Monohydroxy primitive in hydroxyl to can be described as a hydroxyl (- OH) in functional group and monohydroxy primitive be a functional group； In monohydroxy primitive other reactive groups are can be considered with the hydroxyl of other reaction-ity group reactions.

In embodiments of the present invention, the optional supermolecule hydrogen bond action, by being present in dynamic aggregation object The hydrogen bond group of one or more is appointed to participate in main chain/cross-linked network chain backbone, side chain, branch, bifurcated chain, side group, end group It is formed.

The hydrogen bond group preferably comprises following constituent：

At least one of further preferably following constituent：

Wherein,Indicate with polymer chain, be crosslinked and link or the company of any other suitable group (including hydrogen atom) It connects.In embodiments of the present invention, hydrogen bond group can be selected from amide groups, carbamate groups, urea groups, thiocarbamate The derivative etc. of base and the above group.

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：

Contain the organic of at least one of organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali Boron compound (I)；Compound (II) containing monohydroxy primitive；Contain organic boron acidic group, organic boronic ester group, organic halogen simultaneously Change the compound (III) of at least one of boryl, organic boronic alkali and monohydroxy primitive；Contain organic boronic ester bond and its The compound (IV) of his reactive group；Without containing organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic Alkali, monohydroxy primitive and organic boronic ester bond but compound (V) containing other reactive groups；Wherein, organoboration It closes object (I), the compound (II) of the primitive containing monohydroxy and compound (V) and does not prepare the dynamic aggregation object separately as raw material Material.

The organoboron compound (I), the compound (II) containing monohydroxy primitive, compound (III), compound (IV), compound (V) can be the micromolecular compound that molecular weight is no more than 1000Da, can also be that molecular weight is more than The macromolecular compound of 1000Da；In organoboron compound (I), the compound (II) containing monohydroxy primitive, compound (III) In, it can contain or not contain other reactive groups.

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：Hydroxyl, carboxylic Base, carbonyl, acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, sulfydryl, alkenyl, alkynyl, cyano, piperazine base, Oximido, diazanyl, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxy group, acrylate group, acrylamide group, Maleimide base group, succinimide ester groups, norbornene group, azo group, azido group, heterocyclic group, triazole Quinoline diketone, carbon radicals, oxygen radical etc.；It is preferred that hydroxyl, amino, sulfydryl, alkenyl, isocyanate groups, epoxy group, propylene Acid esters group, acrylamide group.

The organoboron compound (I), with following representation：

Wherein, A is the module of organic boronic primitive；M is the number of modules A, m >=1；L is the substituent group on single A, Or the linking group between two or more A, selected from following any or several structures：Molecular weight is no more than The polymer chain residue of the small molecule alkyl of 1000Da, molecular weight more than 1000Da, singly-bound, hetero atom linker, molecular weight are not Divalent or multivalence small molecule alkyl, molecular weight more than 1000Da are more than the divalent or multivalence polymer chain residue of 1000Da；Its In, when m=1, L is the substituent group on individual module A, and small molecule alkyl, the molecule of 1000Da are no more than selected from molecular weight Polymer chain residue at least one of of the amount more than 1000Da；m>When 1, linkers of the L between two or more modules As Group, it is big no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight selected from singly-bound, hetero atom linker, molecular weight In at least one of the divalent of 1000Da or multivalence polymer chain residue；P is the number of group L, p >=1；

The compound (II), with following representation：

Wherein, G is the module containing monohydroxy primitive；N is the number of module G, n >=1；J is the substitution on individual module G Group, or the linking group between two or more module G, selected from following any or several structures：Hydrogen atom, The small molecule alkyl of heteroatom group, molecular weight no more than 1000Da, molecular weight are more than polymer chain residue, the molecule of 1000Da Inorganic molecules chain residue of the amount no more than 1000Da, molecular weight are more than inorganic macromolecular chain residue, singly-bound, the carbon carbon of 1000Da Double bond, triple carbon-carbon bonds, hetero atom linker, molecular weight are big no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight It is residual no more than the divalent of 1000Da or polyvalent mineral small molecule chain in the divalent or multivalence polymer chain residue of 1000Da, molecular weight Base, molecular weight are more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da；Wherein, when n=1, J is on individual module G Substituent group, small molecule alkyl, molecular weight selected from hydrogen atom, heteroatom group, molecular weight no more than 1000Da are more than The inorganic molecules chain residue of polymer chain residue, molecular weight no more than 1000Da, the molecular weight of 1000Da is more than 1000Da's Any one of inorganic macromolecular chain residue is appointed several；n>When 1, linking groups of the J between two or more module G, It is no more than the divalent or multivalence small molecule of 1000Da selected from singly-bound, carbon-carbon double bond, triple carbon-carbon bonds, hetero atom linker, molecular weight The divalent of alkyl, molecular weight more than 1000Da or multivalence polymer chain residue, molecular weight are no more than the divalent or multivalence of 1000Da Inorganic molecules chain residue, molecular weight are more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da；Q is the number of group J, q≥1；

The compound (III), with following representation：

Wherein, A is the module of organic boronic primitive；X is the number of modules A, x >=1；G is the mould containing monohydroxy primitive Block；Y is the number of module G, y >=1；T is between two or more A or between two or more G or between A and G Linking group, selected from following any or several structures：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da's Divalent or multivalence small molecule alkyl, molecular weight are more than the divalent or multivalence polymer chain residue of 1000Da；V is the number of group T, v≥1；

The compound (IV), with following representation：

Wherein, E is the module containing organic boronic ester bond；U is the number of module E, u >=1；Y is taking on individual module E For group, or it is the substituent group on individual module E and the linking group between two or more module E, and at least one Group Y is connected with the boron atom of organic boronic ester bond, and at least one group Y is connected with the carbon atom of organic boronic ester bond；Wherein, Other reactivity for containing at least one other reactive group at least one group Y, and containing in all group Y Group number is more than or equal to 2；The group Y, selected from following any or several structures：Molecular weight is no more than 1000Da's Polymer chain residue, singly-bound, hetero atom linker, the molecular weight of small molecule alkyl, molecular weight more than 1000Da are no more than The divalent or multivalence small molecule alkyl of 1000Da, molecular weight are more than the divalent or multivalence polymer chain residue of 1000Da；Wherein, u When=1, Y is the substituent group on individual module E, big no more than small molecule alkyl, the molecular weight of 1000Da selected from molecular weight In at least one of the polymer chain residue of 1000Da；u>When 1, Y is the substituent group and two or more on individual module E Linking group between module E, the small molecule alkyl, molecular weight selected from molecular weight no more than 1000Da are poly- more than 1000Da It closes at least one of object chain residue and singly-bound, hetero atom linker, molecular weight is small no more than the divalent of 1000Da or multivalence At least one of the divalent of molecule alkyl, molecular weight more than 1000Da or multivalence polymer chain residue；R is the number of group Y, r≥2；

Wherein, the modules A containing organic boron acidic group, can be selected from at least one of lower structure：

Wherein, K₁For 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；Wherein, in A4 Cyclic structure is the nonaro-maticity containing at least one organic boron acidic group or armaticity boron heterocyclic group；Cyclic structure in A4 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 connect with group L or group T-phase；Boron atom in the various structures is at least It is connected by boron carbon key with a carbon atom, and at least one organic group is keyed to by the boron carbon in boron atom；

The modules A containing organic boronic ester group, can be selected from at least one of lower structure：

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 B5 is containing at least one The nonaro-maticity or armaticity boron heterocyclic group of organic boronic ester group；The ring member nitrogen atoms of cyclic structure in B5 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 connects with group L or group T-phase；Boron atom in the various structures at least passes through boron carbon with a carbon atom Key is connected, and at least one organic group is keyed to by the boron carbon in boron atom；

The modules A containing organic halogenation boryl, can be selected from at least one of lower structure：

Wherein, X₁、X₂、X₃、X₄、X₅For halogen atom, at least one of F, Cl, Br, I can be selected from；K₃It is former with boron The group that son is connected directly is selected from following any structure：Hydrogen atom, heteroatom group, molecular weight are no more than 1000Da's Small molecule alkyl, molecular weight are more than the polymer chain residue of 1000Da；Wherein, the cyclic structure in C4 is to have containing at least one The nonaro-maticity or armaticity boron heterocyclic group of machine halogenation boryl；The ring member nitrogen atoms of cyclic structure in C4 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 halogenation boryl, and at least one A ring member nitrogen atoms connect with group L or group T-phase；Boron atom in the various structures at least passes through boron carbon key with a carbon atom It is connected, and at least one organic group is keyed to by the boron carbon in boron atom；

The modules A containing organic boronic alkali, can be selected from at least one of lower structure：

Wherein, M₁ ⁺、M₂ ⁺、M₃ ⁺、M₅ ⁺、M₆ ⁺、M₇ ⁺、M₈ ⁺、M₉ ⁺、M₁₂ ⁺、M₁₄ ⁺、M₁₅ ⁺、M₁₆ ⁺、M₁₈ ⁺、M₁₉ ⁺、M₂₀ ⁺For monovalence sun from Son can be selected from but be not limited only to Li⁺、Na⁺、K⁺、Ni⁺、Ag⁺、NH₄ ⁺；M₄ ²⁺、M₁₀ ²⁺、M₁₁ ²⁺、M₁₇ ²⁺、M₂₁ ²⁺For bivalent cation, It can be selected from but is not limited only to Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺、Fe²⁺、Cu²⁺、Mn²⁺；M₁₃ ³⁺For Tricationic, can be selected from but not It is only limitted to Al³⁺、Fe³⁺；K₄、K₅、K₆For the group being connected directly with boron atom, it is selected from following any structure：It is hydrogen atom, miscellaneous The small molecule alkyl of atomic radical, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；Wherein, Cyclic structure in D12, D13, D14 is the nonaro-maticity containing at least one organic boronic alkali or armaticity boron heterocycle Group；The ring member nitrogen atoms of cyclic structure in D12, D13, D14 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 alkali, and at least one ring member nitrogen atoms and group L or group T-phase Even；Boron atom in the various structures is at least connected with a carbon atom by boron carbon key, and at least one organic group It is keyed in boron atom by the boron carbon；

The module G containing monohydroxy primitive, can be selected from at least one of lower structure：

Wherein, K₇、K₈、K₉、K₁₀For the group being connected directly with carbon atom, it is each independently selected from following any knot Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than the polymer of 1000Da Chain residue, molecular weight are residual more than the inorganic macromolecular chain of 1000Da no more than the inorganic molecules chain residue of 1000Da, molecular weight Base；Wherein, the ring member nitrogen atoms of the cyclic structure in F4, F5 are each independently carbon atom, silicon atom or other hetero atoms, and extremely Few ring member nitrogen atoms are carbon atom and constitute alcoholic extract hydroxyl group, and at least one ring member nitrogen atoms connect with group J or group T-phase；

The module E containing organic boronic ester bond, can be selected from at least one of lower structure：

Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；Indicate with hydrogen atom, polymer chain, be crosslinked link or other The connection of any appropriate group, boron atom and carbon atom are accessed by least one connection in polymer chain respectively, Middle any two or two or moreBridge can be connected into；Wherein structural formula (5) or structural formula (6) if in two carbon atoms it is logical Cross two or moreCirclewise organic boric acid ester structure is connected, then it is heteroatomic hexatomic ring for the 6th atom Or it is arbitrary seven yuan and its above ring；Once B-O-C keys dissociate, the group or segment being preferably connected with C atoms just with B atoms Dissociation, being so conducive to the dynamic aggregation object has better dynamic.

The heteroatom group is selected from following any group：Halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine Base, silicon substrate, phosphorus base, triazole, isoxazoles, amide groups, imide, thioamides base, enamine base, carbonate group, amino first Perester radical, thiocarbamate base, thioester substrate, thio ester group, ortho acid ester group, phosphate-based, phosphorous acid ester group, phosphinate Base, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphoryl, carbon Amide, thioamides, phosphamide, phosphoramidite, pyrophosphoramide, cyclophosphamide, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl Base, peptide bond, diazanyl, hydrazide group, thio carbohydrazide base, azo carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, Thiocarbazates base, carbonohydrazides, thiocarbohydrazide, azo group, urea groups, isourea base, isothiourea group, allophanate group, Thioallophanate base, guanidine radicals, amidino groups, amino guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrous Acyl group, sulfonic group, sulfonate group, sulfinat, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, Malaysia acyl Imines, triazoline diketone；

The molecular weight be no more than 1000Da small molecule alkyl, in the following group it is any, any not It is saturated form, any substituted form, any by hydridization form and combinations thereof：C_1-71Alkyl, ring C_3-71Alkyl, benzene Base, benzyl, aryl；

The molecular weight is more than the polymer chain residue of 1000Da, the carbochain polymer selected from homopolymerization or copolymerized form Residue, heterochain polymer residue, elemento-organic polymer residue；

The molecular weight is no more than the small molecule silylation of 1000Da, any, any in the following group It is unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silicon-carbon alkane chain residue, siloxanes Chain residue, silithiane chain residue, silazane chain residue；

The molecular weight is no more than the inorganic molecules chain residue of 1000Da, any, any in the following group Kind unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silane chain residue, silica Compound chain residue, sulphur silicon compound chain residue, sulfur-nitrogen compound chain residue, phosphazene compound chain residue, phosphoric-oxygenic compound chain Residue, borine chain residue；

The molecular weight is more than the inorganic macromolecular chain residue of 1000Da, any, any in the following group Unsaturated form, any substituted form, any by hydridization form and combinations thereof：Polysilane chain residue, poly- silicon Oxygen alkane chain residue, polysulfide silicon chain residue, polysulfide nitrogen chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene are residual for phosphonitrile chain Base, polyborane chain residue；Or any inorganic macromolecular with residue or any change by surface in the following group The inorganic macromolecular with residue of property：Zeolite-type molecular sieves, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecule Sieve, diamond, graphite, graphene, graphene oxide, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, sulphur Change molybdenum, silica, silicon disulfide, silicon nitride, silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, Glass, quartz, ceramics, boron oxide, nitridation sulphur, calcium silicide, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydrogen Compound, boron nitride, boron carbide, aluminium nitride, diaspore, gibbsite, corundum, titanium dioxide；

The singly-bound, selected from carbon-carbon single bond, carbon oxygen singly-bound, carbon sulphur singly-bound, carbon nitrogen singly-bound, carbon silicon singly-bound, silicon silicon list Key, nitrogen nitrogen singly-bound, silicon nitrogen singly-bound；

The hetero atom linker, selected from following any or several combination：Ether, sulfenyl, thioether group, two Valence tertiary amine groups, trivalent tertiary amine groups, divalent silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalent phosphorus base, three valent phosphors base, divalent boryl, three Valence boryl.

The present invention provides a kind of dynamic aggregation object, and the dynamic aggregation object has line style or cyclic structure, preferably logical At least one of following methods are crossed to be prepared (however, the present invention is not limited thereto)：

The first, participates in reaction by least following components and generates the acquisition of organic boronic ester bond：At least one organoboration Close object (I), the compound (II) of at least one primitive containing monohydroxy；Wherein, organoboron compound (I) and the primitive containing monohydroxy Compound (II) contains at most Liang Ge functional groups；

Second, reaction is participated in by least following components and generates organic boronic ester bond and the acquisition of common covalent bond：At least The compound (II) of a kind of organoboron compound (I) and at least one primitive containing monohydroxy, or at least one organoboron compound (I), the combination of the compound (II) of at least one primitive containing monohydroxy and at least one compound (V)；Wherein, organic boron chemical combination The compound (II) of object (I) and the primitive containing monohydroxy is containing there are one functional group and other reactive groups, compounds (V) Contain at most two other reactive groups；

The third, participates in reaction by least following components and generates the acquisition of organic boronic ester bond：At least one compound (III) or it is at least one organoboron compound (I) or the compound (II) of at least one primitive containing monohydroxy or at least A kind of compound (II) of organoboron compound (I) and at least one primitive containing monohydroxy；Wherein, compound (III), organic boron Compound (I), the compound (II) of the primitive containing monohydroxy 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 (IV), Or itself and at least one compound (V)；Wherein, compound (IV), compound (V) contain at most two other reactive bases Group.

The present invention provides another dynamic aggregation object, and the dynamic aggregation object has a branched structure, preferably by with At least one of lower several ways are prepared (however, the present invention is not limited thereto)：

The first, participates in reaction by least following components and generates the acquisition of organic boronic ester bond：At least one organoboration Close object (I), the compound (II) of at least one primitive containing monohydroxy；Wherein, organoboron compound (I) and the primitive containing monohydroxy At least one compound contains at least three functional groups in compound (II), and a combination thereof does not generate the common of gel point or more Covalent cross-linking；

Second, reaction is participated in by least following components and generates organic boronic ester bond and the acquisition of common covalent bond：At least A kind of organoboron compound (I), the compound (II) of at least one primitive containing monohydroxy；Wherein, organoboron compound (I) and contain At least one compound contains at least one functional group and at least one other reactivity in the compound (II) of monohydroxy primitive Group and the sum of functional group and other reactive group numbers are no less than three, and a combination thereof does not generate the common total of gel point or more Valence is crosslinked；

The third, participates in reaction by least following components and generates organic boronic ester bond and the acquisition of common covalent bond：At least A kind of compound (III), at least one compound (V) or this both, at least one organoboron compound (I) or at least A kind of compound (II) of the primitive containing monohydroxy or at least one organoboron compound (I) and at least one primitive containing monohydroxy Compound (II)；Wherein, compound (III), organoboron compound (I), the primitive containing monohydroxy compound (II) contain extremely More Liang Ge functional groups and the compound (II) of at least one compound (III) or organoboron compound (I) or the primitive containing monohydroxy Containing at least one other reactive group, and a combination thereof does not generate the common covalent cross-linking of gel point or more；

4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (IV), Or itself and at least one compound (V)；Wherein, at least one compound (IV) or at least one compound (V) are containing at least Three other reactive groups, and a combination thereof does not generate the common covalent cross-linking of gel point or more.

The present invention provides another dynamic aggregation object, and the dynamic aggregation object has dynamic crosslinking structure, preferably logical At least one of following methods are crossed to be prepared (however, the present invention is not limited thereto)：

The first, participates in reaction by least following components and generates the acquisition of organic boronic ester bond：At least one organoboration Close object (I), the compound (II) of at least one primitive containing monohydroxy；Wherein, organoboron compound (I) and the primitive containing monohydroxy Compound (II) contains at least two functional groups, and at least one organoboron compound (I) or at least one primitive containing monohydroxy Compound (II) contain 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 organic boronic ester bond and the acquisition of common covalent bond：At least A kind of organoboron compound (I), the compound (II) of at least one primitive containing monohydroxy；Wherein, organoboron compound (I) and contain The sum of functional group that the compound (II) of monohydroxy primitive contains and other reactive group numbers no less than two, and at least one has The functional group and other reactive group numbers that the compound (II) of machine boron compound (I) or at least one primitive containing monohydroxy contains The sum of 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 organic boronic ester bond and the acquisition of common covalent bond：At least A kind of compound (III) or itself and at least one compound (V) or at least one organoboron compound (I) or at least one The chemical combination of the compound (II) of the primitive containing monohydroxy or at least one organoboron compound (I) and at least one primitive containing monohydroxy Object (II)；Wherein, compound (III), organoboron compound (I), the primitive containing monohydroxy compound (II) contain at least two A functional group, and at least one compound (III) or the compound (II) of organoboron compound (I) or the primitive containing monohydroxy contain At least three functional groups, or the compound of at least one compound (III) or organoboron compound (I) or the primitive containing monohydroxy (II) contain at least one other reactive group, and a combination thereof does not generate the common covalent cross-linking of gel point or more；

4th kind, reaction is participated in by least following components and generates common covalent bond acquisition：At least one compound (IV), Or itself and at least one compound (V)；Wherein, compound (IV), compound (V) contain at least two other reactive bases Group, and at least one compound (IV) or at least one compound (V) contain at least three other reactive groups, and its group Close the common covalent cross-linking for not generating gel point or more.

In embodiments of the present invention, the dynamic aggregation object or its composition form can be solution, lotion, Glue, cream, ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, Ionic liquid swell gel), foam etc..

Certain auxiliary agents for adding/using, filler can also be added to collectively constitute in preparation process in dynamic aggregation object Dynamic aggregation object material, but these additives it is not necessary to.

Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, Heat stabilizer, toughener, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, emulsifier, dispersion Agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent；

Wherein, the filler is selected from following any or appoints several：Inorganic non-metallic filler, organic is filled out at metal packing Material.

In embodiments of the present invention, a kind of method of energy-absorbing is provided, which is characterized in that provide a kind of dynamic aggregation object simultaneously Energy-absorbing is carried out using it as energy-absorbing material；Wherein, the dynamic aggregation object is containing organic boronic ester bond and optionally super Molecule hydrogen bond；Wherein, the organic boronic ester bond as dynamic aggregation object polymerization linking point or crosslinking linking point or Person exists as polymerization linking point and crosslinking linking point simultaneously, is the necessary condition to form or maintain dynamic aggregation object structure； And the dynamic aggregation object at least contains 3 organic boronic ester bonds as chain backbone group on any one chain direction；

At least one of wherein, the organic boronic ester bond, have the following structure：

Wherein, at least one carbon atom is connected by boron carbon key with boron atom in the structure, and at least one has Machine group is keyed to by the boron carbon in boron atom；Indicate with hydrogen atom, polymer chain, be crosslinked link or other The connection of any appropriate group, boron atom and carbon atom are accessed by least one connection in polymer chain respectively, Middle any two or two or moreBridge can be connected into；Wherein structural formula (8) or structural formula (9) if in two carbon atoms it is logical Cross two or moreCirclewise organic boric acid ester structure is connected, then it is heteroatomic hexatomic ring for the 6th atom Or it is arbitrary seven yuan and its above ring；Once B-O-C keys dissociate, the group or segment being preferably connected with C atoms just with B atoms Dissociation, being so conducive to the dynamic aggregation object has better dynamic.

In embodiments of the present invention, the dynamic aggregation physical performance is adjustable on a large scale, before having wide application Scape, in the necks such as military aerospace equipment, functional coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material Domain all embodies the application effect to attract people's attention.Specifically, it can be applied to and make damper, padded coaming, shock resistance Protective materials, athletic protective article, army and police's protective article, self-repairability coating, self-repairability plank, self-repairability binder, The products such as bulletproof glass squeegee, toughness material, shape-memory material, force snesor, sealing element, toy.

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

(1) poly- as dynamic reversible key structure dynamic using organic boronic ester bond and optional supermolecule hydrogen bond in the present invention Object is closed, the dynamic of organic boronic ester bond and supermolecule hydrogen bond is taken full advantage of.The dynamic organic boronic ester bond of the present invention has It, can (room temperature or mild heat be not necessarily to catalyst under mild conditions compared with the stronger dynamic reversibility of common dynamic covalent bond Or other stimulations) dynamic reversible reaction occurs, it is poly- with quick selfreparing, the dynamic for recycling recyclable characteristic to obtain Close object；Meanwhile material embodies good cycling processability again, is easily recycled and utilizes again, this is in existing polymeric acceptor It cannot achieve in system.In addition, by optionally controlling other conditions (auxiliary agent, adjustment reaction temperature is such as added), It can accelerate or be quenched dynamic reversible balance under appropriate environment, be at required state, this is in existing supermolecule It is more difficult inside chemistry and dynamic covalent systems to accomplish.Due to without common covalent cross-linking more than gel point, material Material can realize selfreparing, moulding, recycling and reprocessing largely interior so that polymer material has broader application Range and more permanent service life.

(2) in the present invention, using the organic boronic ester bond formed based on monohydroxy, contained compound abundance, knot Structure is clear, and synthesis condition is simple, controllability is high, convenient for carrying out Precise spraying to dynamic aggregation object structure and being conducive to industrial metaplasia The lot stability etc. of production, and low in raw material price, can substantially reduce synthesis cost, be convenient for cost control.

(3) the dynamic aggregation object in the present invention has good Modulatory character.It is used as the compound of raw material by control The parameters such as molecular structure (the especially structure of functional groups of organic boronic primitive and monohydroxy primitive), functional group number, molecular weight, can It prepares with different appearance features, the dynamic aggregation object that performance is adjustable, widely used.Simultaneously as hydrogen bond group has knot Structure diversity can carry out group to the dynamic of polymer in a wider context by controlling the type and number of hydrogen bond group Collocation and regulation and control are closed, based on the difference of itself and organic boronic ester bond dynamic, it is more more that structure more horn of plenty, performance can be obtained Sample, dynamic reversible effect have more the polymer material of hierarchy.By suitable formula combination, can contain in dynamic aggregation object Different organic boronic ester bonds and optional different supermolecule hydrogen bond, generate different dynamic key combinations, and then cooperateed with With orthogonal performance.Larger advantage has been embodied compared with other polymeric materials.

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, it is characterised in that the dynamic aggregation object, wherein containing organic boronic The organic boronic ester bond and optional supermolecule hydrogen bond action that primitive is generated with monohydroxy elementary reaction；Wherein, described to have Machine boric acid ester 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- Close the necessary condition of object structure；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.

Term " polymerization " used is propagation process/effect of chain in the present invention, generally refers to the reaction of lower molecular weight The process that object passes through product of the reaction formations such as polycondensation, addition polymerization, the ring-opening polymerisation synthesis with higher molecular weight.Among these, instead Answer object be typically polymerizing power (can spontaneously be polymerize, or can initiator or it is outer plus under capable of acting on into Row polymerization) the compounds such as monomer, oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize. The product being polymerize by two or more reactant is known as copolymer.It is pointed out that institute in the present invention " polymerization " stated, it includes the linear growth process of reactant molecule chain, include the branched process of reactant molecule chain, including anti- The annulation process of object strand is answered, the cross-linking process of reactant molecule chain is also included.In embodiments of the present invention, " polymerization " Also include chain growth caused by supermolecule hydrogen bond action.

Term " crosslinking " used in the present invention generally refers between reactant molecule and/or in reactant molecule by dynamic The chemistry and/or supramolecular chemistry of state covalent bond and/or supermolecule hydrogen bond connect to be formed with two dimension, three-dimensional cluster type and in turn Form the process of three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction It is long, cluster (can be two dimension or three-dimensional) is gradually formed, developing deeply is three-dimensional infinite network.Unless stated otherwise, of the invention In crosslinking only include gel point or more (contain gel point, similarly hereinafter) three-dimensional infinite network, gel point two dimension below, three-dimensional group The polymer chain architecture that clustering architecture and the degree of cross linking are zero is then non-crosslinking structure.

Heretofore described " gel point ", expression is reactant in cross-linking process, and viscosity is uprushed, and starts to coagulate Gelatinization phenomenon starts reflecting point when crosslinking reaches a three-dimensional infinite network, also referred to as percolation threshold for the first time.In gel point There is above cross-linking products three-dimensional infinite network structure, cross-linked network to constitute an entirety and across entire polymer knot Structure, cross-linked structure are relatively stable and secured；It is only loose link structure, not in gel point cross-linking products below Three-dimensional infinite network structure is formed, is only locally lying in a small amount of two dimension or three-dimensional net structure, and is not belonging to across entire poly- Close 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..Described in the present invention is " dynamic State covalent bond " refers to the special covalent bond of one kind that can carry out reversible fracture and formation under optimum conditions, in the present invention Refer in particular to organic boronic ester bond.

Wherein, " linear structure ", refer to the presentation of dynamic aggregation object strand is rule or irregular length Chain is linear, and the side group in polymer molecular chain does not exist generally with branch, generally by many repetitive units in a continuous length On be formed by connecting；For " linear structure ", be usually by the monomer without long-chain side group by polycondensation reaction, sudden reaction or The polymerizations such as ring-opening reaction are formed.

Wherein, " cyclic structure " refers to that dynamic aggregation object strand exists in the form of closed chain comprising The cyclic structure of the forms such as monocycle, polycyclic, bridged ring, nested rings；For " cyclic structure ", line style or branched polymeric can be passed through The intramolecular cyclization of object is formed, and can also be prepared by the methods of ring expansion polymerization reaction.

Wherein, " branched structure " refers to containing side chain, branch and bifurcated chain on dynamic aggregation object strand Etc. structures, include but are not limited to the structures such as star-like, H-type, combed, dendritic, hyperbranched and combinations thereof and its with line style, Cyclic structure is further combined, such as line style chain end connection ring shape structure, cyclic structure are combined with comb-type structure, dendritic Chain end connects endless chain, etc.；For " structures such as side chain, branch and bifurcated chain of polymer ", there can be 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 side Method is many, is generally well known to those skilled in the art, such as can carry out polycondensation reaction by the monomer containing long-chain side group It is formed, is either formed by the chain transfer reaction of free radical in addition polymerization process or by radiating and chemically reacting in line style Extend branched structure on strand to be formed.

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, " cross-linked structure " refers to that dynamic aggregation object has three-dimensional unlimited reticular pattern structure, is usually By the components such as the monomer containing functional group/other reactive groups that can participate in cross-linking reaction or prepolymer participate in homopolymerization, It is copolymerized, or is formed by the cross-linking reaction between polymer chain linearly or nonlinearly.

Can also be that there are many topologys in addition, can only have a kind of polymer of topographic morphologies in a polymer composition The mixture of the polymer of form.

The dynamic aggregation object can contain organic boric acid ester on any appropriate position of polymer chain skeleton Key, you can, can also be on polymer side chain backbone containing organic to contain organic boronic ester bond on main polymer chain skeleton Boric acid ester bond；Contain organic boronic ester bond between polymer chains on cross linked chain synthetism frame that can also be；The present invention is also not excluded for Contain organic boronic ester bond in the side group of polymer chain and/or end group, but at least contains 3 works on any one chain direction For the organic boronic ester bond of chain backbone group；Wherein, preferably in noncrosslinking main polymer chain skeleton and cross-linked network chain backbone It is upper to contain organic boronic ester bond.The organic boronic ester bond in general, can carry out reversible fracture and regeneration； Under the conditions of suitable, the organic boronic ester bond of any position can participate in dynamic reversible exchange in dynamic aggregation object.It needs to refer to Go out, the organic boronic ester bond on main polymer chain/cross-linked network skeleton carries out dynamic reversible exchange and is conducive to described move State polymer obtains the dynamic characteristics such as more excellent selfreparing, recyclable.

Wherein, for non-crosslinking structure, the polymer chain skeleton include main polymer chain skeleton and polymer lateral chain, The skeleton of the chains such as branch, bifurcated chain；Wherein, if not otherwise indicated, the side chain in the polymer of branched structure, branch, bifurcated chain Also it can be considered main chain, the polymer especially for hyperbranched, dendroid and containing such structural unit；Side chain, branch, bifurcated Group on the skeleton of chain both can be considered the side group of main chain, also can be considered (side chain, branch, bifurcated chain) backbone radical.For Dynamic aggregation object with non-crosslinking structure, by organic boronic ester bond and/or supermolecule hydrogen bond come build dynamic covalently and/or Supermolecule hydrogen bond polymerize, and when generating shear thickening behavior, can generate sticky enhancing, but not generate visco-elastic transformation, Be conducive to generate complete viscous loss.

Wherein, for cross-linked structure, the polymer chain skeleton refers to being present in the arbitrary segment in cross-linked network Skeleton, wherein cross-linked network chain backbone are known as cross-linked network skeleton, and cross-linked network skeleton includes the cross linked chain between polymer chain Synthetism frame, the crosslinking link between polymer chain can be an atom, a singly-bound, a group, a segment, a group Cluster etc.；Side chain, branch, the bifurcated chain of cross-linked network chain backbone also have chain backbone.For the dynamic aggregation object with cross-linked structure, It constitutes dynamic covalent cross-linking and/or supermolecule hydrogen bond crosslinks by organic boronic ester bond and/or supermolecule hydrogen bond, wherein dynamic The degree of cross linking of state covalent cross-linking and supermolecule hydrogen bond crosslinks can be more than respective gel point, can also be in respective gel point Hereinafter, the degree of cross linking of dynamic covalent cross-linking is preferably more than its gel point.When the crosslinking of organic boronic ester bond reaches gel point or more When, when as stress/strain response materials'use, it is better able to embody the advantage of its dynamic, such as generate shearing When thickening characteristic, the transformation of strong viscous liquid and elastic solid (Hookean body) can be generated, it is steady to be conducive to holding structure while energy-absorbing It is fixed.

Wherein, " side chain " refers to being connected with main polymer chain skeleton in dynamic aggregation object structure and divide Cloth is in the chain structure that the molecular weight of main chain backbone side is more than 1000Da；Wherein, " branch ", " bifurcated chain " refer to from The molecular weight that main polymer chain skeleton or any other chain bifurcated come out is more than the chain structure of 1000Da；For the sake of simplicity, side chain, Molecular weight when being more than 1000Da of branch, bifurcated chain, if not otherwise indicated, is then collectively referred to as side chain.Wherein, " the side Base " refers to being connected with polymer chain skeleton in dynamic aggregation object structure and is distributed in the molecular weight of chain backbone side not Chemical group and molecular weight higher than 1000Da are not higher than the short-side chain of 1000Da.For " side chain " and " side group ", can have Multilevel hierarchy namely side chain can continue to carry side group and side chain, and the side chain of side chain can continue have side group and side chain, therein Side chain also includes branch and bifurcated chain isodesmic structure.Wherein, " end group " refers in dynamic aggregation object structure with poly- Conjunction object chain backbone is connected and positioned at the chemical group of chain backbone end；In the present invention, side group can also have end under specific condition Base.

In one embodiment of the invention, the dynamic aggregation object has non-crosslinking structure, wherein containing described Organic boronic ester bond but do not contain hydrogen bond.

In one embodiment of the invention, the dynamic aggregation object has non-crosslinking structure, wherein containing described Organic boronic ester bond and hydrogen bond.

In another embodiment of the invention, the dynamic aggregation object has cross-linked structure, wherein containing described Organic boronic ester bond but do not contain hydrogen bond, wherein the degree of cross linking based on organic boronic ester bond is more than gel point.

In another embodiment of the invention, the dynamic aggregation object has cross-linked structure, wherein containing described Organic boronic ester bond and hydrogen bond, the wherein degree of cross linking of organic boronic ester bond and hydrogen bond are in its respective gel point hereinafter, but two The sum of degree of cross linking of person is more than the gel point of dynamic aggregation object.

In another embodiment of the invention, the dynamic aggregation object has cross-linked structure, wherein containing described Organic boronic ester bond and hydrogen bond, the wherein degree of cross linking of organic boronic ester bond are in its gel point hereinafter, the degree of cross linking of hydrogen bond is solidifying at it It is more than glue point.

In another embodiment of the invention, the dynamic aggregation object has cross-linked structure, wherein containing described More than its gel point, the degree of cross linking of hydrogen bond is solidifying at it for organic boronic ester bond and hydrogen bond, the wherein degree of cross linking of organic boronic ester bond Below glue point.

In another embodiment of the invention, the dynamic aggregation object has cross-linked structure, wherein containing described Organic boronic ester bond and hydrogen bond, the wherein degree of cross linking of organic boronic ester bond and hydrogen bond are more than its respective gel point.

In embodiments of the present invention, the dynamic organic boronic ester bond is by organic boronic primitive and monohydroxy primitive It reacts, wherein the organic boronic primitive is selected from but is not limited only to organic boron acidic group, organic boronic ester group, organic halogenation Boryl, organic boronic alkali and combinations thereof；It is preferred that using organic boron acidic group and monohydroxy primitive, organic boronic ester group and monohydroxy Primitive forms organic boric acid ester key, more preferably forms organic boric acid ester key using organic boron acidic group and monohydroxy primitive；It adopts Form organic boric acid ester key with monohydroxy elementary reaction with organic boron acidic group and/or organic boronic ester group has on preparation method Unique advantage, as raw material is easy to get, preparation condition is simple and practicable.

The organic boronic alkali refers to being made of boron atom, a negative oxygen ion being connected with the boron atom Structural motif (B-O^-) and including at least a cation (Mⁿ⁺, it is monovalence, divalent or Tricationic, is selected from but not It is only limitted to Li⁺、Na⁺、K⁺、Ni⁺、Ag⁺、NH₄ ⁺、Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺、Fe²⁺、Cu²⁺、Mn²⁺、Al³⁺、Fe³⁺), and it is therein Boron atom 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 the present invention, a negative oxygen ion (- O in organic boronic alkali^-) it is a functional group.

The optional supermolecule hydrogen bond action in the present invention, is established by any appropriate by hydrogen bond group Supermolecular mechanism, the hydrogen atom being covalently attached to generally by the atom Z big with electronegativity and electronegativity are big, radius is small Atom Y, using hydrogen as medium, generates the hydrogen bond link of Z-H ... Y shape formulas, wherein described Z, the Y is any appropriate between Z and Y Electronegativity is 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；Z, Y is selected from O, N atomic time, contained compound Abundance, hydrogen bond are easily formed and dynamic is strong.Wherein, the supermolecule hydrogen bond action preferably as supermolecule polymerization and/ Or crosslinking and/or chain in ring formation exist namely hydrogen bond can only play connect two or more chain segment units play Increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond and only play the crosslinking of interchain supermolecule, or only plays chain Two or more arbitrary combination in interior ring formation or three of the above.Hydrogen bond action is not excluded in the present invention to play The effect 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, such readily available required dynamic and required Intensity.

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 preferably comprises following constituent：

At least one of further preferably following constituent：

In the present invention, the hydrogen bond group can be only present on polymer chain skeleton, can also exist only in poly- It closes in object chain side group, can also exist simultaneously on skeleton and side group.When existing simultaneously when on skeleton and side group, in specific feelings Under condition, skeleton hydrogen bond group can form hydrogen bond between the hydrogen bond group of side.Side hydrogen bond group have structure diversity, including but It is not limited to hydrogen bond donor and receptor number, group size, the length linked and rigidity between polymer chain；In addition, polymerization The quantity of the side hydrogen bond group connected on object chain is also a wide range of adjustable.It participates in forming hydrogen bond crosslinks with side hydrogen bond group, can obtain Intensity, dynamic, response, crosslink density adjustable hydrogen bond crosslinks on a large scale, while by pair being linked with polymer chain Regulation and control, can control the dynamic of hydrogen bond, glass transition temperature of cross-linked polymer etc., and then effectively regulate and control dynamic aggregation Every dynamic property of object.

Wherein, the skeleton hydrogen bond group is to be present on polymer chain skeleton (including side chain/branch/bifurcated chain bone On frame) hydrogen bond group, wherein at least part of atoms is the component part of chain backbone.Suitable skeleton hydrogen bond group citing is such as (but the present invention is not limited only to this)：

Wherein, the side group hydrogen bond group is the hydrogen bond group in polymeric chain (including side chain) side group, wherein pendant hydrogen Key group also is present on the multilevel hierarchy of side group.Suitable side group hydrogen bond group may include having the skeleton hydrogen bond base The group of unity structure, more specifically suitable side group hydrogen bond group 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 in dynamic aggregation object into the covalent polymerized/cross-linked of Mobile state During generate；Can also be to be generated in advance after supermolecule hydrogen bond action again into the covalent polymerized/cross-linked of Mobile state；It can also be After the covalent polymerized/cross-linked of dynamic is formed, supermolecule hydrogen bond action, but the present invention are generated during dynamic aggregation object subsequent forming It is not limited only to this.

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, and common covalently polymerization is formed between compound and/or its reaction product.

Described in the present invention contains organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali At least one of organoboron compound (I), can following representation：

Wherein, A is the module of organic boronic primitive；M is the number of modules A, m >=1；L is the substituent group on individual module A Group, or the linking group between two or more modules As；P is the number of group L, p >=1.

The modules A containing organic boron acidic group, can be selected from at least one of lower structure：

Wherein, K₁For 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；Wherein, in A4 Cyclic structure is that the nonaro-maticity containing at least one organic boron acidic group or armaticity boron heterocyclic group, boron atom are placed in cyclic annular knot In structure, cyclic structure can be small molecule ring, can also be macromolecular ring, be preferably 3~100 membered rings, more preferably 3~50 Membered ring, more preferably 3~10 membered rings；The ring member nitrogen atoms of cyclic structure in A4 be each independently carbon atom, boron atom or its His hetero atom, and at least one ring member nitrogen atoms are boron atom and constitute organic boron acidic group, and at least one ring member nitrogen atoms and group L It is connected；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in A4 can be substituted, and can not also be substituted；Ring-type in A4 Structure can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Expression and base The connection of group L；Boron atom in the various structures is at least connected with a carbon atom by boron carbon key, and at least one has Machine group is keyed to by the boron carbon in boron atom.

Wherein, the cyclic structure in A4 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：

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 B5 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 B5 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 are connected with group L；Cyclic annular knot in B5 Hydrogen atom on each ring member nitrogen atoms of structure can be substituted, and can not also be substituted；Cyclic structure in B5 can be monocycle knot Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Indicate the connection with group L；It is described each Boron atom in kind structure is at least connected with a carbon atom by boron carbon key, and at least one organic group passes through the boron Carbon is keyed in boron atom.

Wherein, the cyclic structure in B5 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：

Wherein, X₁、X₂、X₃、X₄、X₅For halogen atom, at least one of F, Cl, Br, I can be selected from；K₃It is former with boron The group that son is connected directly is selected from following any structure：Hydrogen atom, heteroatom group, molecular weight are no more than 1000Da's Small molecule alkyl, molecular weight are more than the polymer chain residue of 1000Da；Wherein, the cyclic structure in C4 is to have containing at least one The nonaro-maticity or armaticity boron heterocyclic group, boron atom of machine halogenation boryl are placed in cyclic structure, and cyclic structure can be small Molecular Ring can also be macromolecular ring, be preferably 3~100 membered rings, more preferably 3~50 membered rings, more preferably 3~10 yuan Ring；The ring member nitrogen atoms of cyclic structure in C4 are each independently carbon atom, boron atom or other hetero atoms, and it is at least one at Annular atom is boron atom and constitutes organic halogenation boryl, and at least one ring member nitrogen atoms are connected with group L；Cyclic structure in C4 Hydrogen atom on each ring member nitrogen atoms can be substituted, and can not also be substituted；Cyclic structure in C4 can be single ring architecture, Multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Indicate the connection with group L；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 C4 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：

Wherein, M₁ ⁺、M₂ ⁺、M₃ ⁺、M₅ ⁺、M₆ ⁺、M₇ ⁺、M₈ ⁺、M₉ ⁺、M₁₂ ⁺、M₁₄ ⁺、M₁₅ ⁺、M₁₆ ⁺、M₁₈ ⁺、M₁₉ ⁺、M₂₀ ⁺For monovalence sun from Son can be selected from but be not limited only to Li⁺、Na⁺、K⁺、Ni⁺、Ag⁺、NH₄ ⁺；M₄ ²⁺、M₁₀ ²⁺、M₁₁ ²⁺、M₁₇ ²⁺、M₂₁ ²⁺For bivalent cation, It can be selected from but is not limited only to Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺、Fe²⁺、Cu²⁺、Mn²⁺；M₁₃ ³⁺For Tricationic, can be selected from but not It is only limitted to Al³⁺、Fe³⁺；K₄、K₅、K₆For the group being connected directly with boron atom, it is selected from following any structure：It is hydrogen atom, miscellaneous The small molecule alkyl of atomic radical, molecular weight no more than 1000Da, molecular weight are more than the polymer chain residue of 1000Da；Wherein, Cyclic structure in D12, D13, D14 is the nonaro-maticity containing at least one organic boronic alkali or armaticity boron heterocycle Group, boron atom is 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 rings；The ring member nitrogen atoms of cyclic structure in D12, D13, D14 Carbon atom, boron atom or other hetero atoms are each independently, and at least one ring member nitrogen atoms are boron atom and constitute organic boron Hydrochlorate base, and at least one ring member nitrogen atoms are connected with group L；On each ring member nitrogen atoms of cyclic structure in D12, D13, D14 Hydrogen atom can be substituted, and can not also be substituted；Cyclic structure in D12, D13, D14 can be single ring architecture, polycyclic knot Structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Indicate the connection with group L；In the various structures 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.

Wherein, the cyclic structure in D12, D13, D14 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：Boron heterocycle alkane, boron heterocyclic hydrocarbon, the miscellaneous benzene of boron, the miscellaneous naphthalene of boron, boron are miscellaneous Miscellaneous luxuriant and rich with fragrance, the boron heteroaryl hydrocarbon of anthracene, boron；The preferred boron heterocycle pentane of listed cyclic structure, boron azacyclohexane, boron heterocycle hexene, boron heterocycle Hexadiene, boron heterocycle hexenone, the miscellaneous benzene of boron.Citing is such as：

In the present invention, in the modules A containing organic boronic primitive, at least one hydroxyl can be connected in a boron atom simultaneously At least two in base, an ester group, at least one halogen atom, at least one negative oxygen ion, it can also in the same module Contain at least one boron hydroxyl, at least one boric acid ester group, at least one halogen atom, at least one negative oxygen ion simultaneously, lifts Such as：

Compound simultaneously containing in organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali extremely Few two kinds help 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 dynamic of dynamic aggregation object The performances such as state property.

In the present invention, when the modules A of the organic boronic primitive is present in polymer, and there are two or multiple institutes When stating connection, it can be connected to not cyclic or not at the side that cyclic annular or cluster in the polymer chain of cluster, can also be connected to In base/side chain；When only there are one the connection when, any position of polymer chain can be connected to.

As m=1, p=1 or 2, L are the substituent group on individual module A；As p=2, L can be selected from same knot Structure or a variety of different structures；The L structures can be selected from following any or appoint several：Molecular weight is no more than small point of 1000Da Sub- alkyl, molecular weight are more than the polymer chain residue of 1000Da.Suitable organoboron compound (I) structure example formed is such as Under：

Wherein, g, h, j are each independently a fixed value or average value, g >=1, h >=1, j >=1.

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.

Work as m>When 1, modules A can be selected from same structure or a variety of different structures, at this time p >=1, and L is two or more moulds Linking group between block A；As p >=2, L can be selected from same structure or a variety of different structures；The L structures can be selected from It is any below or appoint it is several：Singly-bound, hetero atom linker, molecular weight are no more than the divalent or multivalence small molecule hydrocarbon of 1000Da Base, molecular weight are more than the divalent or multivalence polymer chain residue of 1000Da.

When L is selected from singly-bound, boron boron singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond, boron can be selected from Nitrogen singly-bound；Preferably boron boron singly-bound, boron carbon single bond, carbon-carbon single bond.Suitable organoboron compound (I) structure example formed is such as Under：

Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.

When L 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；Hetero atom linker is preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups.What is formed suitably has Machine boron compound (I) structure example is as follows：

When L, 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；L 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 organoboron compound (I) structure example formed is as follows：

Can be any appropriate two when L, 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 Closing 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 L is selected from divalent or multivalence carbochain polymer residue, can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, any taken For form or any by hydridization form：Divalent or multivalence polyolefins chain residue, as divalent or multivalence Polyethylene Chain residue, Divalent or multivalence polypropylene chains residue, divalent or multivalence polyisobutene chain residue, divalent or multivalence polystyrene chain residue, divalent Or multivalence polyvinyl chloride chain residue, divalent or multivalence Vingon chain residue, divalent or multivalence polyvinyl fluoride chain residue, divalent Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalent or multivalence polytrifluorochloroethylene chain residue, divalent or multivalence polyvinyl acetate chain Residue, divalent or multivalence polyvinyl alcohol chain residue, divalent or multivalence Polyvinylalkylethers chain residue, divalent or multivalence polybutadiene The poly- drop of alkene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence polychlorobutadiene chain residue, divalent or multivalence Bornylene chain residue etc.；Divalent or multivalence polyacrylic chain residue, such as divalent or multivalence polyacrylic acid chain residue, divalent or more Valence polyacrylamide chain residue, divalent or multivalence polymethyl acrylate chain residue, divalent or multivalence polymethyl methacrylate chain Residue etc.；Divalent or multivalence polypropylene nitrile chain residue, such as divalent or multivalence polyacrylonitrile chain residue.L preferred divalent or more Valence Polyethylene Chain residue, divalent or multivalence polypropylene chains residue, divalent or multivalence polystyrene chain residue, divalent or multivalence polychlorostyrene Ethylene chain residue, divalent or multivalence polybutadiene chain residue, divalent or multivalence polyisoprene chain residue, divalent or multivalence poly- third Olefin(e) acid chain residue, divalent or multivalence polyacrylamide chain residue, divalent or multivalence polyacrylonitrile chain residue.What is formed suitably has Machine boron compound (I) structure example is as follows：

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。

When L 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.； Divalent or multivalence sulfur-containing polymer chain residue, such as divalent or multivalence polysulfones chain residue, divalent or multivalence polyphenylene sulfide chain residue. The preferred divalent of L 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 organoboron compound (I) structure example formed is as follows：

Can be any appropriate macromolecular main chain master when L is selected from divalent or element of multivalence organic polymer residue The polymer residue to be made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, can be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalent or Multivalence silicone-based polymers chain residue, such as divalent or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane Chain residue, divalent or multivalence poly-organosilicon borine chain residue, divalent or multivalence poly-organosilicon azane chain residue, divalent or multivalence are poly- Organic silithiane chain residue, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or the poly- organic metal siloxane chain of multivalence Residue；Divalent or multivalence organic boron Type of Collective object chain residue, as the divalent or poly- organo-borane chain residue of multivalence, divalent or multivalence are poly- Organic boron azane chain residue, divalent or the poly- organic boron sulfane chain residue of multivalence, divalent or the poly- organic boron phosphine chain residue of multivalence etc.； Divalent or multivalence organic phosphates polymer chain residue；Divalent or multivalence Organic leadP Type of Collective object chain residue；Divalent or multivalence are organic Tin Type of Collective object chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain residue；Divalent or multivalence antimony organic Type of Collective object chain are residual Base.The preferred divalent of L or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence are poly- Organo-borane chain residue.Suitable organoboron compound (I) structure example formed is as follows：

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

The compound (II) containing monohydroxy primitive in the present invention, can use following representation：

Wherein, G is the module containing monohydroxy primitive；N is the number of module G, n >=1；J is the substitution on individual module G Group, or the linking group between two or more module G；Q is the number of group J, q >=1.

The module containing monohydroxy primitive can be selected from the monohydroxy primitive without cyclic structure and/or contain The monohydroxy primitive of cyclic structure, can be selected from at least one of lower structure：

Wherein, K₇、K₈、K₉、K₁₀For the group being connected directly with carbon atom, it is each independently selected from following any knot Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than the polymer of 1000Da Chain residue, molecular weight are residual more than the inorganic macromolecular chain of 1000Da no more than the inorganic molecules chain residue of 1000Da, molecular weight Base；Wherein, the cyclic structure in F4, F5 is that the saturation containing at least one hydroxyl or unsaturated cyclic group, carbon atom are placed in In cyclic structure, cyclic structure can be small molecule ring, can also be macromolecular ring, be preferably 3~100 membered rings, more preferably For 3~50 membered rings, more preferably 3~10 membered rings；The ring member nitrogen atoms of cyclic structure in F4, F5 be each independently carbon atom, Silicon atom or other hetero atoms, and at least one ring member nitrogen atoms are carbon atom and constitute alcoholic extract hydroxyl group, and at least one ring member nitrogen atoms It is connected with group J；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in F4, F5 can be substituted, and can not also be substituted； Cyclic structure in F4, F5 can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested rings knot Structure；Indicate the connection with group J and any twoIt can be connected on the carbon atom that the same non-hydroxyl is connected directly.

When the cyclic structure in F4, F5 be selected from containing there are one hydroxyl saturation or unsaturated cyclic group when, selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Cycloalkanes, ring Hydrocarbon, oxa- cycloalkanes, azacycloalkyl, sulfur heterocyclic alkyl, phospha cycloalkanes, boron heterocycle alkane, benzene, naphthalene, anthracene, phenanthrene, aromatic hydrocarbons；Listed cyclic annular knot Structure optimization cyclopentane, hexamethylene, cyclohexene, cyclohexadiene, cyclonene, benzene, oxinane, oxocane, oxa- ring Dodecane, piperidine, Azacyclooctane, azepine cyclododecane.Citing is such as：

It, can be with when the cyclic structure in F4, F5 is selected from saturated cyclic group containing two or more hydroxyls It can not also contain hetero atom containing hetero atom；When the cyclic structure in F4, F5 is selected from the saturation containing two or more hydroxyls When naphthenic base, the linker between each two hydroxyl group at least contains 4 carbon atoms, such as：

When the cyclic structure in F4, F5 is selected from the saturated heterocyclic alkyl containing two or more hydroxyls, each two Linker between hydroxyl group at least contains 3 (carbon atom and hetero atom) atoms, each two hydroxyl base when including hetero atom Linker between group at least contains 4 carbon atoms when not including hetero atom (containing only carbon atom), such as：

It, can when the cyclic structure in F4, F5 is selected from the unsaturated cyclic group containing two or more hydroxyls Hetero atom can not also be contained to contain hetero atom, the linker between each two hydroxyl group at least contains when containing unsaturated bond 3 (carbon atom and/or hetero atom) atoms, the linker between each two hydroxyl group without containing unsaturated bond but contain miscellaneous original The period of the day from 11 p.m. to 1 a.m at least contains 3 atoms (carbon atom and hetero atom), and the linker between each two hydroxyl group does not contain unsaturated bond And at least contain 4 carbon atoms when without containing hetero atom, such as：

In the present invention, when described, the module G containing monohydroxy primitive is present in polymer, and there are two or it is multiple When the connection, it can be connected to not cyclic or not cyclic annular or cluster at that in the polymer chain of cluster, can also be connected to In side group/side chain；When only there are one the connection when, any position of polymer chain can be connected to.

As n=1, q=1,2 or 3, J are the substituent group on individual module G；As q=2 or 3, J can be selected from together A kind of structure or a variety of different structures；The J structures can be selected from following any or appoint several：Hydrogen atom, heteroatom group, Small molecule alkyl of the molecular weight no more than 1000Da, polymer chain residue, molecular weight of the molecular weight more than 1000Da are no more than Inorganic molecules chain residue, the molecular weight of 1000Da are more than the inorganic macromolecular chain residue of 1000Da.The base containing monohydroxy The unitary alcoholic compound that the compound (II) of member can form line style, saturation or unsaturated cyclic structure can also be formed containing full And/or the polyol compound of unsaturated cyclic structure, form the unitary alcoholic compound of line style, saturation or unsaturated cyclic structure Structure example is as follows：

Wherein, x, y are each independently a fixed value or average value, x >=1, y >=1.It is formed containing saturation or unsaturation The polyol compound of cyclic structure is exemplified below：

The structure of the compound (II) of the primitive containing monohydroxy of the example above is only that the primitive containing monohydroxy is better described Compound (II) with this condition possessed by typical structure and propose, only thus under the conditions of it is more representational some knot Structure rather than limiting the scope of the present invention.

Work as n>When 1, module G can be selected from same structure or a variety of different structures, at this time q >=1, and J is two or more moulds Linking group between block G, the compound (II) of the primitive containing monohydroxy is polyol compound at this time；As q >=2, J It can be selected from same structure or a variety of different structures；The J structures can be selected from following any or appoint several：Singly-bound, carbon carbon Double bond, triple carbon-carbon bonds, hetero atom linker, molecular weight are big no more than the divalent of 1000Da or multivalence small molecule alkyl, molecular weight It is residual no more than the divalent of 1000Da or polyvalent mineral small molecule chain in the divalent or multivalence polymer chain residue of 1000Da, molecular weight Base, molecular weight are more than the divalent or polyvalent mineral macromolecular chain residue of 1000Da.

When J is selected from singly-bound, carbon-carbon single bond, carbon oxygen singly-bound, carbon sulphur singly-bound, carbon nitrogen singly-bound, carbon silicon singly-bound, silicon can be selected from Silicon singly-bound, nitrogen nitrogen singly-bound, silicon nitrogen singly-bound；It is preferred that carbon-carbon single bond, carbon oxygen singly-bound, carbon sulphur singly-bound.When J is selected from carbon-carbon single bond linker When connecting monohydroxy primitive models G, the carbon atom of the linker between each two hydroxyl group in each monohydroxy primitive models Number is at least 4.Compound (II) structure example of the suitable primitive containing monohydroxy formed is as follows：

Wherein, g is a fixed value or average value, g >=2.

When J is selected from carbon-carbon double bond, triple carbon-carbon bonds, hydroxyl group should be in the two of double bond plane when selected from carbon-carbon double bond Compound (II) structure example of side, the suitable primitive containing monohydroxy of formation 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；Hetero atom linker is preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups.It is formed suitably containing single Compound (II) structure example of hydroxyl primitive 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；Particularly, when the molecular weight is small no more than the divalent of 1000Da or multivalence When molecule alkyl is selected from saturated alkyl chain, at least contain 2 carbon atoms：Two to one hundred four ten tetravalence C_1-71Alkyl, two to one hundred 40 tetravalence ring C_3-71Alkyl, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred four ten tetravalence aryl；J preferably two is arrived Sexavalence ethyl, two arrive octavalence propyl, and two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valence cyclopenta, two to ten two Valence cyclohexyl, two arrive sexavalence phenyl.Compound (II) structure example of the suitable primitive containing monohydroxy formed is as follows：

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 acetate 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 polyacrylic acid hydroxy methacrylate, divalent or Multivalence polyacrylamide chain residue, divalent or multivalence polymethyl acrylate chain residue, divalent or multivalence polymethyl methacrylate Chain residue, divalent or multivalence polymethylacrylic acid hydroxy methacrylate chain residue etc.；Divalent or multivalence polypropylene nitrile chain residue, such as two Valence or multivalence polyacrylonitrile chain residue etc..The preferred divalent of J or multivalence Polyethylene Chain residue, divalent or multivalence polypropylene chains residue, Divalent or multivalence polystyrene chain residue, divalent or multivalence polyvinyl chloride chain residue, divalent or multivalence polybutadiene chain residue, two Valence or multivalence polyisoprene chain residue, divalent or multivalence polyacrylic acid chain residue, divalent or multivalence polyacrylic acid hydroxy methacrylate, Divalent or multivalence polymethylacrylic acid hydroxy methacrylate chain residue divalent or multivalence polyacrylamide chain residue, divalent or multivalence poly- third Alkene nitrile chain residue.Compound (II) structure example of the suitable primitive containing monohydroxy formed 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.； Divalent or multivalence sulfur-containing polymer chain residue, such as divalent or multivalence polysulfones chain residue, divalent or multivalence polyphenylene sulfide chain residue. The preferred divalent of J or multivalence polyethylene oxide chain residue, divalent or multivalence polypropylene oxide chain residue, divalent or the poly- tetrahydrochysene furan of multivalence It mutters chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalent or multivalence makrolon Chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence polysulfones chain residue, divalent or multivalence are poly- Urethane chain residue.Compound (II) structure example of the suitable primitive containing monohydroxy formed is as follows：

Wherein, f, g, h, i, j, k are each independently a fixed value or average value, preferably f >=36, g >=36, h >=36, i≥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 boron azane chain residue, divalent or the poly- organic boron sulfane chain residue of multivalence, divalent or the poly- organic boron phosphine chain residue of multivalence etc.； Divalent or multivalence organic phosphates polymer chain residue；Divalent or multivalence Organic leadP Type of Collective object chain residue；Divalent or multivalence are organic Tin Type of Collective object chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain residue；Divalent or multivalence antimony organic Type of Collective object chain are residual Base.The preferred divalent of J or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence are poly- Organo-borane chain residue.Compound (II) structure example of the suitable primitive containing monohydroxy formed 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.The preferred divalent of J or multivalence silane chain residue, divalent or multivalence silicon oxide compound chain residue, divalent or multivalence phosphonitrile Compound chain residue, divalent or multivalence borine chain residue.Compound (II) structure of the suitable primitive containing monohydroxy formed is lifted Under such as：

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 for phosphonitrile chain residue, divalent or multivalence polyborane chain residue.The preferred divalent of J or multivalence polysilane chain Residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence polyphosphazene chain residue, divalent or multivalence polyborane chain residue. Compound (II) structure example of the suitable primitive containing monohydroxy formed is as follows：

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 fiber, carbon nanotube, fullerene, 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.Graphite that J is modified preferably through surface, by table The graphene of face modification, the carbon fiber being modified by surface, the carbon nanotube being modified by surface, the dioxy being modified by surface SiClx, by surface be modified silicon nitride, by surface be modified silicon carbide, by surface be modified silicate, by surface Modified glass fibre, the boron nitride being modified by surface.Compound (II) citing of the suitable primitive containing monohydroxy formed Such as：The carbon of graphene, surface with monohydroxy primitive of graphite, surface of the surface with monohydroxy primitive with monohydroxy primitive Fiber, surface carry the carbon nanotube of monohydroxy primitive, surface carries the silicon carbide of monohydroxy primitive, surface carries monohydroxy base Silicate, surface glass fibre with monohydroxy primitive of the silica, surface of member with monohydroxy primitive.

Contain organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic while described in the present invention The compound (III) of at least one of alkali and monohydroxy primitive, can following representation：

Wherein, A is the module of organic boronic primitive, is specifically defined and can refer to determining for modules A in organoboron compound (I) Justice, which is not described herein again, wherein A is preferably the module containing organic boron acidic group and/or organic boronic ester group；X is modules A Number, x >=1；As x >=2, modules A can be selected from same structure or a variety of different structures；G is the mould containing monohydroxy primitive Block is specifically defined the definition of module G in the compound (II) for can refer to the primitive containing monohydroxy, and which is not described herein again；Y is module The number of G, y >=1；As y >=2, module G can be selected from same structure or a variety of different structures；T between two or more A, Or the linking group between two or more G or between A and G；When T is between two or more A or two or more When linking group between a G, T needs the definition for meeting L the or J linkers, and which is not described herein again；T structures can be selected from Under it is any or appoint it is several：Singly-bound, hetero atom linker, molecular weight no more than 1000Da divalent or multivalence small molecule alkyl, Molecular weight is more than the divalent or multivalence polymer chain residue of 1000Da；V is the number of group T, v >=1；As v >=2, T can be selected from Same structure or a variety of different structures.

When T is selected from singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond, boron nitrogen singly-bound, boron can be selected from Silicon singly-bound, silicon silicon singly-bound, silicon-carbon singly-bound, silicon nitrogen singly-bound；Preferably carbon-carbon single bond, boron carbon single bond.The suitable compound formed (III) structure example is as follows：

The structure of the compound (III) of the example above is only that compound (III) is better described with this condition to be had Typical structure and propose, only thus under the conditions of some more representational structures, rather than the limit to the scope of the present invention It is fixed.

When T 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；Hetero atom linker is preferably ether, sulfenyl, divalent tertiary amine groups, trivalent tertiary amine groups.Suitableization formed It is as follows to close object (III) structure example：

When T, 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；T 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 (III) structure example formed is as follows：

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, or several monomers, The copolymer of oligomer or polymer composition；Polymer chain can be flexible chain or rigid chain.

When T is selected from divalent or multivalence carbochain polymer residue, can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, any taken For form or any by hydridization form：Divalent or multivalence polyolefins chain residue, as divalent or multivalence Polyethylene Chain residue, Divalent or multivalence polypropylene chains residue, divalent or multivalence polyisobutene chain residue, divalent or multivalence polystyrene chain residue, divalent Or multivalence polyvinyl chloride chain residue, divalent or multivalence Vingon chain residue, divalent or multivalence polyvinyl fluoride chain residue, divalent Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalent or multivalence polytrifluorochloroethylene chain residue, divalent or multivalence polyvinyl acetate chain Residue, divalent or multivalence 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, such as divalent or multivalence polyacrylic acid chain residue, divalent or multivalence hydroxyethyl acrylate, divalent or more Valence poly hydroxy ethyl acrylate, 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, as divalent or multivalence are poly- Acrylonitrile chain residue etc..The preferred divalent of T or multivalence Polyethylene Chain residue, divalent or multivalence polypropylene chains residue, divalent or multivalence Polystyrene chain residue, divalent or multivalence polyvinyl chloride chain residue, divalent or multivalence polybutadiene chain residue, divalent or multivalence are poly- Isoprene chain residue, divalent or multivalence polyacrylic acid chain residue, divalent or multivalence polyacrylamide chain residue, divalent or multivalence Polyacrylonitrile chain residue.Suitable compound (III) structure example formed is as follows：

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

When T 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.； Divalent or multivalence sulfur-containing polymer chain residue, such as divalent or multivalence polysulfones chain residue, divalent or multivalence polyphenylene sulfide chain residue. The preferred divalent of T or multivalence polyethylene oxide chain residue, divalent or multivalence polypropylene oxide chain residue, divalent or the poly- tetrahydrochysene furan of multivalence It mutters chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalent or multivalence makrolon Chain residue, divalent or multivalence polyethylene terephthalate chain residue, divalent or multivalence polysulfones chain residue, divalent or multivalence are poly- Urethane chain residue.Compound (II) structure example of the suitable primitive containing monohydroxy formed is as follows：

Can be any appropriate macromolecular main chain master when T is selected from divalent or element of multivalence organic polymer residue The polymer residue to be made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, can be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalent or Multivalence silicone-based polymers chain residue, such as divalent or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane Chain residue, divalent or multivalence poly-organosilicon borine chain residue, divalent or multivalence poly-organosilicon azane chain residue, divalent or multivalence are poly- Organic silithiane chain residue, divalent or the poly- organophosphor siloxane chain residue of multivalence, divalent or the poly- organic metal siloxane chain of multivalence Residue；Divalent or multivalence organic boron Type of Collective object chain residue, as the divalent or poly- organo-borane chain residue of multivalence, divalent or multivalence are poly- Organic boron azane chain residue, divalent or the poly- organic boron sulfane chain residue of multivalence, divalent or the poly- organic boron phosphine chain residue of multivalence etc.； Divalent or multivalence organic phosphates polymer chain residue；Divalent or multivalence Organic leadP Type of Collective object chain residue；Divalent or multivalence are organic Tin Type of Collective object chain residue；Divalent or multivalence organo-arsenic Type of Collective object chain residue；Divalent or multivalence antimony organic Type of Collective object chain are residual Base.The preferred divalent of T or multivalence poly-organosilicon alkane chain residue, divalent or multivalence polysiloxane chain residue, divalent or multivalence are poly- Organo-borane chain residue.Suitable compound (III) structure example formed is as follows：

It should be noted that when the compound (II) of the group L in organoboron compound (I) structure, the primitive containing monohydroxy When the group T in group J, compound (III) structure in structure is selected from the chain structure in addition to cyclic structure, group A can It is connected to the end of L, is also connected to any position in L；Group G may connect to the end of J, be also connected to appointing in J Meaning position；Group A and G may connect to the end of T, be also connected to any position in T.When organoboron compound (I) structure In group L, the primitive containing monohydroxy compound (II) structure in group J, the group T in compound (III) structure be selected from When two dimension or three-dimensional cluster structure, the cluster structure is generally formed by common covalent bond, the organic boron in cluster structure Acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali and monohydroxy primitive hydroxyl be usually dispersed in outside cluster It encloses and only carries out dynamic aggregation/cross-linking reaction in cluster periphery.Therefore, dynamic of the dynamic aggregation object obtained contained by it After reversible organic boronic ester bond dissociation, that is, it is dissociated into cluster unit.

Compound (II), compound (III), wherein organic boronic for organoboron compound (I), the primitive containing monohydroxy Any one ester group in any one hydroxyl, organic boronic ester group in base, has any one halogen atom in organic halogenation boryl Any one hydroxyl in any one negative oxygen ion, monohydroxy primitive in machine boric acid alkali is a functional group.For organic The compound (II) of boron compound (I), the primitive containing monohydroxy can be simple function group, difunctional, trifunctional or more officials Compound can be rolled into a ball, for example, being for structure

Organoboron compound (I), be respectively simple function group, difunctional, trifunctional, four-functional group；For another example It is for structure

The primitive containing monohydroxy compound (II), be respectively simple function group, difunctional, trifunctional, tetrafunctional Group；Can be difunctional, trifunctional or polyfunctional compound, for example, being for structure for compound (III)

Compound (III), be respectively difunctional, trifunctional, four-functional group, five functional groups.

It is organic in addition to containing in organoboron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III) Outside hydroxyl in boronate, organic boronic ester group, organic halogenation boryl, organic boronic alkali, monohydroxy primitive, it is also an option that Property contain other reactive groups.

Other heretofore described reactive groups, refer to can spontaneously, or can initiator or light, The group for the common covalent bond that chemical reaction generates in addition to organic boronic ester bond is carried out under the conditions of heat, irradiation, catalysis etc.；Properly Group citing such as：Hydroxyl, carboxyl, acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, sulfydryl, alkenyl, It is alkynyl, cyano, piperazine base, oximido, diazanyl, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxy group, acrylate-based Group, folds acrylamide group, maleimide base group, n-hydroxysuccinimide group, norbornene group, azo group Nitrogen groups, heterocyclic group etc.；The preferred hydroxyl of other reactive groups, carboxyl, amino, sulfydryl, alkenyl, isocyanate groups, ring Oxygen groups, acrylate group, acrylamide group.As an example, the suitable structure in part provides in the preceding example.

Other described reactive groups in the present invention, play the role of in system, first, performing the derivatization anti- The dynamic aggregation object that functionalization (such as hydrophobicity, fluorescence, inoxidizability functional characteristic) should be prepared, second is that in the chemical combination Object itself or its between other compounds or react with it between product directly by the anti-of other reactive groups Common covalent bond should be formed, so that the molecular weight of the compound and/or its reaction product increase/degree of functionality increases, is promoted Into the crosslink density for forming the dynamic aggregation object and/or the increase dynamic aggregation object with dynamic crosslinking structure. In the present invention, the common covalent linkage set up by other reactive group polymerized/cross-linkeds, it is necessary to assure obtained polymer The degree of cross linking is less than gel point so that when the organic boronic ester bond in dynamic aggregation object dissociates, polymeric system can be dissociated into more Small unit achievees the purpose that recyclable or rebuilds.It should be noted that all " other reactivity occurred in the present invention Group " is only used for performing the derivatization and/or being formed common covalent linkage.

The compound (IV) containing organic boronic ester bond He other reactive groups described in the present invention, can be as Lower structure indicates：

Wherein, E is the module containing organic boronic ester bond；U is the number of module E, u >=1；Y is taking on individual module E For group, or it is the substituent group on individual module E and the linking group between two or more module E, and at least one Group Y is connected with the boron atom of organic boronic ester bond, and at least one group Y is connected with the carbon atom of organic boronic ester bond；Wherein, Other reactivity for containing at least one other reactive group at least one group Y, and containing in all group Y Group number is more than or equal to 2；R is the number of group Y, r >=2.

The module E containing organic boronic ester bond, at least one of structure as follows：

In the present invention, the module E containing organic boronic ester bond, can through the invention in any for being previously mentioned Kind or appoint several organic boronic primitive A and it is any or appoint several module G containing monohydroxy primitive by monohydroxy primitive with Obtained by organic boron acidic group, organic boronic ester group, organic halogenation boryl, the condensation reaction of organic boronic alkali or exchange reaction.

As u=1, Y is the substituent group on individual module E, and Y can be selected from same structure or a variety of different structures, and And the quantity of other reactive groups that contains of Y and structure must assure that can obtain the dynamic aggregation object；The Y knots Structure can be selected from following any or appoint several：Small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are more than 1000Da's Polymer chain residue.

Work as u>When 1, module E can be selected from same structure or a variety of different structures, and Y is the substituent group on individual module E Linking group between two or more module E, Y can be selected from same structure or a variety of different structures, and Y contain its The quantity and structure of his reactive group, which must assure that, can obtain the dynamic aggregation object；The Y structure can be selected from point At least one of small molecule alkyl of the son amount no more than 1000Da, the polymer chain residue of molecular weight more than 1000Da and list The divalent of key, hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are more than the two of 1000Da At least one of valence or multivalence polymer chain residue.

For the compound (IV) containing organic boronic ester bond He other reactive groups, generally contain organic boronic The monomer of ester bond, the oligomer containing organic boronic ester bond, the prepolymer containing organic boronic ester bond.Compound (IV) can pass through It is prepared by any appropriate method, include by the compound (II) of suitable organoboron compound (I) and the primitive containing monohydroxy into It is prepared by row.

Heretofore described compound (V), is not particularly limited its structure, and any appropriate does not contain organic boron Acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali, monohydroxy primitive and organic boronic ester bond but contain The optional compound (V) as in the present invention of the compound of other reactive groups.

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.

Heretofore described dynamic aggregation object material is not limited only to carry out using above-described several embodiments It prepares, can also be the combination of above-mentioned several embodiments or itself and other kind of embodiment.In every case sharp in embodiments Organoboron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III), compound (IV) is used to be carried out as raw material Prepare dynamic aggregation object, no matter it is in the form of raw material, or also or is to close in the form of the compound of synthesis material It ought to be included in the present invention's since it according to the present invention can instruct to be obtained at the form of the intermediate product of polymer In scope of patent protection.Similarly, those skilled in the art according to the present invention can also instruct, and reasonably utilize above-mentioned several Kind compound is implemented to obtain the dynamic aggregation object.

The heteroatom group being previously mentioned in the present invention can be any appropriate containing heteroatomic group, can Selected from following any group, but the present invention is not limited only to this：Halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine groups, silicon substrate, phosphorus It is base, triazole, isoxazoles, amide groups, imide, thioamides base, enamine base, carbonate group, carbamate groups, thio Carbamate groups, thioester substrate, thio ester group, ortho acid ester group, phosphate-based, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate ester It is base, phosphoryl, phosphorous acyl group, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphoryl, carbamide, thio Amide, phosphamide, phosphoramidite, pyrophosphoramide, cyclophosphamide, ifosfamide, thio-phosphamide, rhizome of Chinese monkshood acyl group, peptide bond, hydrazine Base, hydrazide group, thio carbohydrazide base, azo carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, the thio first of diazanyl Perester radical, carbonohydrazides, thiocarbohydrazide, azo group, urea groups, isourea base, isothiourea group, allophanate group, ghiourea group formic acid Ester group, guanidine radicals, amidino groups, amino guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic acid Base, sulfonate group, sulfinat, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide, triazole Quinoline diketone.

The molecular weight being previously mentioned in the present invention is no more than the small molecule alkyl of 1000Da, typically contains 1 to 71 carbon Atom can contain heteroatom group, and can be free of has heteroatom group.Generally, the small molecule alkyl can be selected from By it is any in the following group, any it is unsaturated in the form of, it is any substituted form, any by hydridization form and its group It closes：C_1-71Alkyl, ring C_3-71Alkyl, phenyl, benzyl, aryl；Small molecule alkyl is preferably methyl, ethyl, propyl, propylene, fourth Base, butylene, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl；More preferably methyl, ethyl, propyl, benzene Base.

The molecular weight being previously mentioned in the present invention is more than the polymer chain residue of 1000Da, can be any appropriate polymerization Object chain residue includes but are not limited to carbochain polymer residue, heterochain polymer residue, elemento-organic polymer residue.Wherein, Polymer can be homopolymer, or appoint the copolymer of several monomers, oligomer or polymer composition；Polymer chain can be flexibility Chain or rigid chain.

Wherein, the carbochain polymer residue can be any appropriate macromolecular main chain mainly by carbon atom structure At polymer residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form, It is any by hydridization form and combinations thereof：Polyolefins chain residue, such as Polyethylene Chain residue, polypropylene chains residue, poly- isobutyl Alkene chain residue, polystyrene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain residue, polytetrafluoro Ethylene chain residue, polytrifluorochloroethylene chain residue, polyvinyl acetate chain residue, Polyvinylalkylethers chain residue, polybutadiene Alkene chain residue, polyisoprene chain residue, polychlorobutadiene chain residue, polynorbornene chain residue etc.；Polyacrylic chain is residual Base, as polyacrylic acid chain residue, polyacrylamide chain residue, polymethyl acrylate chain residue, polymethyl methacrylate chain are residual Base etc.；Polypropylene nitrile chain residue, such as polyacrylonitrile chain residue；It is preferred that Polyethylene Chain residue, polypropylene chains residue, polyphenyl second Alkene chain residue, polyvinyl chloride chain residue, polybutadiene chain residue, polyisoprene chain residue, polyacrylic acid chain residue, polypropylene Amide chain residue, polyacrylonitrile chain residue.

The heterochain polymer residue, can be any appropriate macromolecular main chain mainly by carbon atom and nitrogen, oxygen, The polymer residue that the hetero atoms such as sulphur are constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, it is any It is substituted form, any by hydridization form and combinations thereof：Polyethers chain residue, such as polyethylene oxide chain residue, polycyclic oxygen Propane chain residue, PolyTHF chain residue, asphalt mixtures modified by epoxy resin fat chain residue, phenolic resin chain residue, polyphenylene oxide chain residue etc.；Polyester Class chain residue, such as polycaprolactone chain residue, poly- valerolactone chain residue, polylactide chain residue, polyethylene terephthalate Chain residue, unsaturated polyester (UP) chain residue, alkyd resin chain residue, polycarbonate chain residue, Biopolvester chain residue, liquid crystal polyester Chain residue etc.；Polyamine class chain residue, as polyamide chains residue, polyimides chain residue, polyurethane chain residue, polyureas chain residue, Polysulfide is for carbamic acid ester chain residue, Lauxite chain residue, melamine resin chain residue etc.；Liquid crystal polymer chain residue；Sulfur-bearing Polymer chain residue, such as polysulfones chain residue, polyphenylene sulfide chain residue；It is preferred that polyethylene oxide chain residue, PolyTHF chain Residue, asphalt mixtures modified by epoxy resin fat chain residue, polycaprolactone chain residue, polylactide chain residue, polyamide chains residue, polyurethane chain residue, Polyureas chain residue；The heterochain polymer residue can react shape by click-reaction, such as CuAAC reactions, thiol-ene At.

The elemento-organic polymer residue can be any appropriate macromolecular main chain mainly by silicon, boron, aluminium etc. The hetero atoms such as inorganic elements hetero atom and nitrogen, oxygen, sulphur, phosphorus constitute polymer residue, can be selected from it is any in the following group, appoint It is a kind of unsaturated form, any substituted form, any by hydridization form and combinations thereof：Silicone-based polymers Chain residue, such as poly-organosilicon alkane chain residue, polysiloxane chain residue, poly-organosilicon borine chain residue, poly-organosilicon azane Chain residue, poly-organosilicon sulfane chain residue, poly- organophosphor siloxane chain residue, poly- organic metal siloxane chain residue；Organic boron Type of Collective object chain residue, such as poly- organo-borane chain residue, poly- organic boron sulfane chain residue, poly- have poly- organic boron azane chain residue Machine boron phosphine chain residue etc.；Organic phosphates polymer chain residue；Organic leadP Type of Collective object chain residue；Organic tin polymer chain is residual Base；Organo-arsenic Type of Collective object chain residue；Antimony organic Type of Collective object chain residue；It is preferred that poly-organosilicon alkane chain residue, poly organo Alkane chain residue, poly- organo-borane chain residue.

The molecular weight being previously mentioned in the present invention is no more than the small molecule silylation of 1000Da, can be any appropriate The small molecule silylation that molecular backbone is mainly made of the hetero atoms such as silicon atom and nitrogen, oxygen, sulphur, phosphorus, generally, described is small Molecule silylation 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：Silicon-carbon alkane chain residue, siloxane chain residue, silithiane chain residue, silazane chain residue；It is preferred that silicon-carbon alkane chain Residue, siloxane chain residue.

The molecular weight being previously mentioned in the present invention is no more than the inorganic molecules chain residue of 1000Da, can be arbitrary conjunction What suitable molecular backbone and side chain was mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic molecules chain residue, generally, the inorganic molecules chain residue can be selected from any in the following group, any Unsaturated form, any substituted form or any by hydridization form：Silane chain residue, silicon oxide compound chain are residual Base, sulphur silicon compound chain residue, sulfur-nitrogen compound chain residue, phosphazene compound chain residue, phosphoric-oxygenic compound chain residue, borine chain Residue；It is preferred that silane chain residue, silicon oxide compound chain residue, phosphazene compound chain residue, borine chain residue.

The molecular weight being previously mentioned in the present invention is more than the inorganic macromolecular chain residue of 1000Da, can be any appropriate Macromolecular main chain and side chain be mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic macromolecular chain residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted shape It is formula, any by hydridization form and combinations thereof：Polysilane chain residue, polysiloxane chain residue, polysulfide silicon chain residue, polysulfide nitrogen Chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene are for phosphonitrile chain residue, polyborane chain residue；Also selected from the following group In any inorganic macromolecular with residue or any inorganic macromolecular with residue being modified by surface：Zeolite type Molecular sieve, aluminium phosphate molecular sieve, phosphoric acid zirconium molecular sieve, heteropolyacid salt molecular sieve, diamond, graphite, graphene, graphite oxide Alkene, carbon nanotube, fullerene, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, silica, silicon disulfide, silicon nitride, Silicon carbide, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, nitridation sulphur, silicon Change calcium, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, water aluminium Stone, gibbsite, corundum, titanium dioxide；It is preferred that polysilane chain residue, polysiloxane chain residue, polyphosphazene chain residue, polyborane chain Residue, by surface be modified graphene, by surface be modified carbon nanotube, by surface be modified carbon fiber, by table The silica of face modification, the silicon nitride being modified by surface, the silicon carbide being modified by surface, the silicic acid being modified by surface Salt, the glass fibre being modified by surface, the boron nitride being modified by surface.

The structure of small molecule alkyl, polymer chain residue, inorganic macromolecular chain residue is not particularly limited, it can To 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, the chain with cyclic structure, two and three dimensions cluster type and combinations thereof；It is residual in small molecule alkyl, polymer chain In base, inorganic macromolecular chain residue, soft segment can be contained, can also contain rigid chain segment, can also simultaneously contain it is flexible and Rigid chain segment.

Heretofore described " singly-bound ", refer in compound molecule between two atoms to share pair of electrons and The common covalent bond constituted, can be selected from carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond.

Heretofore described " hetero atom linker ", can be it is any appropriate contain heteroatomic linking group, It can be selected from following any or appoints 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, divalent boryl, trivalent boryl.

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.

The single ring architecture that is previously mentioned in the cyclic structure of the present invention refers in cyclic structure containing only there are one ring, Citing is such as：

The multiring structure being previously mentioned is referred to containing two or more independent rings in cyclic structure, be illustrated such as：

The spirane structure being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing one The cyclic structure of a atomic building, citing is such as：

The condensed cyclic structure (it also includes two rings, virtue and ring structure) being previously mentioned, refers in cyclic structure containing by two A or multiple rings are to each other by sharing the cyclic structure of two adjacent atomic buildings, and citing is such as：

The caged scaffold being previously mentioned refers to containing in cyclic structure by two or more rings to each other by sharing two The cyclic structure of a above adjacent atomic building, has three-dimensional cage structure, citing is such as：

The nested ring structure being previously mentioned refers in cyclic structure containing connected or embedding to each other by two or more rings The cyclic structure constituted is covered, citing is such as：

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_1-10Indicate " there is 1 to 10 carbon atom ", C_3-20Indicate " there is 3 to 20 A carbon atom "." undersaturated C_3-20Alkyl " refers to C_3-20Compound containing unsaturated bond in alkyl." substituted C_3-20Alkyl " Refer 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 miscellaneous The compound that atom replaces.When a group can be selected from C_1-10When alkyl, it can be selected from any in range shown in subscript The alkyl of carbon atom number, you can be selected from C₁、C₂、C₃、C₄、C₅、C₆、C₇、C₈、C₉、C₁₀Any alkyl in alkyl.In the present invention, In the case of being not particularly illustrated, indicate to can be selected from any integer within the scope of this with the subscript that range format marks, the range Including 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 R₁, 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.

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".For example, " described in specification Organic boronic ester bond as dynamic aggregation object polymerization linking point and/or crosslinking linking point and exist " in "and/or", contain Justice, which is the organic boronic ester bond, to be existed as the polymerization linking point of dynamic aggregation object, or as dynamic aggregation object Crosslinking linking point and exist, or simultaneously as the polymerization linking point of dynamic aggregation object and crosslinking linking point and exist.At this The conjunction "and/or" occurred elsewhere in description of the invention, represents such meaning.

It is used to prepare the organoboron compound (I) of dynamic aggregation object, compound (II), the compound of the primitive containing monohydroxy (III), compound (IV), compound (V), can be gas, liquid, crystal, powder, particle, glue, paste etc..

During preparing dynamic aggregation object, as having in the organoboron compound (I) of raw material, compound (III) Machine boric acid primitive can be deposited in the form of organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali .Organic boronic primitive in organoboron compound (I) with organic boronic ester group, organic halogenation boryl, have ylboronic acid alkali In the presence of form, during being reacted with the compound (II) of the primitive containing monohydroxy, compound (III), Ke Yixian It reacts to form organic boronic by hydrolyzing to form free boric acid, then with the compound (II) of the primitive containing monohydroxy, compound (III) Ester bond；Compound (II), the compound of the reaction and the primitive containing monohydroxy such as ester exchange reaction, condensation reaction can also directly be passed through (III) organic boric acid ester key is formed.

For simultaneously containing in organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic boronic alkali at least A kind of and monohydroxy primitive compound (III) generally requires by controlling reaction condition and the suitable reaction of addition Auxiliary agent enables the monohydroxy primitive in compound (III) and organic boron that is of the same race or not containing in same compound (III) Acidic group member carries out reaction and forms organic boric acid ester key, to obtain dynamic aggregation object.In one polymerization system, except one can be contained Kind or multiple compounds (III) outside, can also contain simultaneously one or more kinds of organoboron compounds (I) and/or it is a kind of or The compound (II) of a variety of primitives containing monohydroxy of person.When raw material is selected from compound (III), to ensure the stability of raw material, change The organic boronic primitive closed in object (III) is preferentially selected with the shape of organic boronic ester group, organic halogenation boryl, organic boronic alkali Formula exists, and exists most preferably in the form of organic boronic ester group.In view of prepared by compound (III) and preserve process relatively It is complicated, is accordingly used in preparing the raw material components of dynamic aggregation object preferentially in organoboron compound (I) and the primitive containing monohydroxy Collocation selection is carried out in compound (II).

In embodiments of the present invention, the compound (II) for organoboron compound (I), the primitive containing monohydroxy, change Object (III) is closed, during forming dynamic monomer and/or prepolymer and/or polymer, in addition to using containing in compound Monohydroxy primitive and/or outside organic boronic primitive reacted, can also simultaneously can using other reactive groups that it contains Selection of land and other compositions are commonly covalently attached such as compound (IV) and/or compound (V) by polymerisation, common anti- Dynamic aggregation object should be constituted.It can also be by organoboron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III) It participates in the prepolymer formed and/or polymer is blended with other compositions such as compound (IV) and/or compound (V), then pass through The common covalent linkage of other compositions forms dynamic aggregation object.It can also be initially formed common covalent linkage, it is organic to re-form dynamic Boric acid ester bond.

For compound (IV), generally by the phase between other reactive groups contained in compound (IV) Mutual reactance, or by other reactive groups contained in compound (IV) with compound (V) and/or by organic boron chemical combination Object (I), the compound (II) of the primitive containing monohydroxy, compound (III) participate in contained in the prepolymer and/or polymer that are formed Other reactive groups between react to each other, to obtain the dynamic aggregation object containing organic boronic ester bond.It can also be straight It connects other reaction-ity group reactions contained in itself by compound (IV) and forms common covalent linkage.Certainly, the present invention not only limits In 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, so that preparation process is simple, raw convenient for high-volume Production, including but not limited to isocyanate group and amino, hydroxyl, the reacting of sulfydryl, acrylate reactions, thiol-ene are clicked instead It answers.

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.

The melt polymerization being previously mentioned in above-mentioned polymerization technique, common implementation are that raw materials of compound is in molten Melt under state, polymerize using the conditions such as initiator or light, heat, irradiation, catalysis, obtains the dynamic aggregation object of molten condition； The polymerisation in solution being previously mentioned, common implementation are that raw materials of compound, initiator are dissolved in appropriate solvent to polymerize Obtain dynamic aggregation object；The interfacial polymerization being previously mentioned, common implementation are that raw materials of compound is dissolved in two kinds mutually not In the solvent to mix, (or interface organic phase side) is polymerize to obtain dynamic aggregation object on the interface of solution；It is previously mentioned Bulk polymerization, common implementation be by raw materials of compound under the conditions ofs a small amount of initiator or light, heat, irradiation, catalysis etc. It is polymerize to obtain dynamic aggregation object；The suspension polymerisation being previously mentioned, common implementation are will to be dissolved with the change of initiator It closes raw material and stirs into droplet, be suspended in aqueous medium and polymerize to obtain dynamic aggregation object；The emulsion polymerization being previously mentioned, Common implementation is to be dispersed in raw materials of compound in the aqueous medium dissolved with initiator by the effect of emulsifier, is formed It is polymerize to obtain dynamic aggregation object again after lotion；The slurry polymerization being previously mentioned, common implementation are by compound original Material is dissolved in appropriate solvent, and initiator is then present in solvent and is polymerize in the form of dispersion, obtained dynamic aggregation object It is precipitated in the form of precipitation；The gas-phase polymerization being previously mentioned, common implementation be by raw materials of compound under gas phase state, It is polymerize to obtain dynamic aggregation object using the conditions such as initiator or light, heat, irradiation, catalysis.

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 constitute the organic boron acidic group of organic boronic ester bond of dynamic aggregation object, organic boronic ester group, Organic halogenation boryl, organic boronic alkali, due to electron deficient possessed by boron atom in group so that it is not easily by containing total Bonding is generated with nucleopilic reagent institute's attack of electronics pair；And for constituting the monohydroxy primitive of organic boronic ester bond, due to oxygen Contain unshared electron pair on atom, with organic boron acidic group, organic boronic ester group, organic halogenation boryl, organic borate During base is in contact, organic boric acid ester key can be formed by reactions such as condensation reaction, ester exchange reactions, it is dynamic to constitute State polymer.

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), foam etc., wherein the dissolvable small-molecular-weight component content one contained in ordinary solid and foam As be not higher than 10wt%, and the small-molecular-weight component content contained in gel generally be not less than 50wt%.When as ordinary solid, It usually has the performances such as more excellent structural stability, mechanical performance, ageing-resistant, can also be by the dynamic aggregation The dynamic aggregation object for obtaining a series of mechanical properties adjustable (from softness to firm) is adjusted in the structure of object, and application range is contained Common civil goods is covered to high-precision military project product, is had wide range of applications.As elastomer, usually more general solid is more soft It is soft, more significant deformation can occur under smaller stress, this is conducive to it and obtains preferable self-repairability, especially The strong dynamic of dynamic organic boronic ester bond based on the present invention；Meanwhile elastomer generally has preferable flexibility and elasticity, this So that it has unique advantage in buffering, damping, shock resistance etc., be based particularly on supermolecule hydrogen bond of the invention optional and Dynamic organic boronic ester bond is as the shock resistance energy absorption capacity that can be sacrificed key and have；In addition, elastomer also has good appearance The advantages that texture, sense of touch is mild, easy coloring, and color sensation is mild and chemical-resistant is good.As gel, it typically is soft to consolidate Body, this makes it have advantageous advantage in terms of selfreparing, is based particularly on the dynamic organic boronic ester bond of the present invention Strong dynamic；Gel (especially hydrogel) is generally also provided with preferable biocompatibility, this makes it in biomedical work There is advantage outstanding in terms of journey；Gel also has excellent damping, damping, shock resistance simultaneously, is based particularly on this hair Bright optional supermolecule hydrogen bond and dynamic organic boronic ester bond are as the shock resistance energy absorption capacity that can be sacrificed key and have.As foam When material, one side advantageously reduces the apparent density of material, is on the other hand particularly conducive in buffering, damping, shock resistance Etc. applied because other than the deformation of foam itself can generate buffering, damping, shock resistance and other effects, the present invention Organic boronic ester bond and optional hydrogen bond action in the dynamic aggregation object can generate the energy of intelligence under stress Amount absorbs and dispersion effect.Based on above feature, the form of dynamic aggregation object of the present invention or its composition is preferably common (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid are molten for solid, elastomer, gel Swollen gel) and foam.

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, starch elder generation and mixed with polymers, put in water after being shaped to product, then by product It handles repeatedly, solable matter is dissolved out to get to open-celled foam product；(4) hollow microsphere method, i.e., in being added in the plastic Become obturator-type foamed plastics through solidification after empty microballoon；Wherein, preferably by dissolving in inert gas and low boiling in the polymer The method of point liquid foams.Using physical blowing method, have operation Poisoning smaller, foaming raw material cost is relatively low, foaming The advantages that agent noresidue 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 Add the method for chemical foaming agent to foam, be conducive to reduce energy consumption in this way and the more fine and close foaming body of abscess can be obtained.

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.

In the preparation process of dynamic aggregation object material, the certain auxiliary agents for adding/using being added can improve Material preparation process improves product quality and yield, reduces product cost or assign product certain distinctive application performance.Institute The auxiliary agent for adding/using stated is selected from following any or several auxiliary agents：Additive synthesis, including catalyst, initiator；Surely Surely change auxiliary agent, including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve processing The auxiliary agent of performance, including lubricant, releasing agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent, dynamic regulation Agent；Change the auxiliary agent of surface property, including antistatic agent, emulsifier, dispersant；Change the auxiliary agent of coloured light, including colorant, glimmering Optical brightener, delustering agent；Fire retardantization and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickening Agent, levelling agent.

Catalyst in the auxiliary agent for adding/using can reduce reaction activation by changing reaction path It can accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalysis Agent：1. polyurethane catalyst for synthesizing：Amines catalyst, as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxies) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (two Methylaminopropyl) diisopropanolamine (DIPA), N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyl cyclohexyl amines, N, N, N ', N '-tetramethyls Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethylethanolamines, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyls caproic acid, N, N- Dimethyl benzylamine, N, N- dimethyl cetylamines etc.；Organometallic catalysts, as stannous octoate, dibutyltin dilaurate, Dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, acetic acid Benzene mercury, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；2. polyolefin catalyst for synthesizing：Such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, four chlorinations Titanium, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, three oxidations Two antimony, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc.；3. CuAAC catalytic reactions Agent：Concerted catalysis is shared by monovalence copper compound and amine ligand；Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH₃CN)₄]PF₆、[Cu(CH₃CN)₄]OTf、CuBr (PPh₃)₃Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yls) methyl] amine (TBTA), three [(the tertiary fourths of 1- Base -1H-1,2,3- triazole-4-yls) methyl] amine (TTTA), three (2- benzimidazoles methyl) amine (TBIA), hydration bathophenanthroline two Sodium sulfonate 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, triethanolamine, triethylamine, pyridine, 4- bis- Dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01- 0.5wt%.

Initiator in the auxiliary agent for adding/using, can cause monomer molecule in polymerization process It activates and generates free radical, improve reaction rate, reaction is promoted to carry out, include but are not limited to following any or appoint several draw Send out agent：1. radical polymerization shares initiator：Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), peroxide Change bis- (4- tert-butylcyclohexyls) esters of two diisopropyl carbonates, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tertiary butyl Peroxide benzoate, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo Object is closed, such as azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；② Living polymerization initiator：Such as 2,2,6,6- tetramethyl -1- oxygroups piperidines, 1- chloro-1-phenyls ethane/stannous chloride/bis- pyridines Ternary system etc.；3. ionic polymerization initiator：Such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, butter of tin/halogen For alkane system etc.；4. coordination polymerization initiator：Such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane body System etc.；5. ring-opening polymerisation initiator：Such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Its In, the preferred lauroyl peroxide of initiator, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used It is not particularly limited, generally 0.1-1wt%.

Antioxidant in the auxiliary agent for adding/using can delay the oxidation process of polymer material, ensure Material can successfully be processed and extend its service life, include but are not limited to following any or appoint several antioxygens Agent：Hinered phenols, such as 2,6- di-tert-butyl-4-methy phenols, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyls of 2- methyl) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyls Base phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl- 6- tert-butyl phenols]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros are equal Triazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamines, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.

Light stabilizer in the auxiliary agent for adding/using can prevent polymer material from light aging occurs, and extend Its service life comprising but be not limited only to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide Titanium, zinc oxide, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxies two Benzophenone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) benzo three Azoles, 2,4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethyls Own ester；Pioneer's type ultra-violet absorber, such as the p- tertiary butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as Bis- (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl esters), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light Stabilizer, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2, 2,6,6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- bis- uncles Butyl benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamates, N, the positive two thio ammonia of fourth positive group of N '-two Base nickel formate etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, Light stabilizer dosage used is not particularly limited, generally 0.01-0.5wt%.

Heat stabilizer in the auxiliary agent for adding/using enables to polymer material processing or using Chemical change does not occur because heated in journey, or delays these variations to achieve the purpose that prolong the service life comprising but It is not limited only to following any or appoints several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, disalt Base lead stearate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organotin Compounds, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double maleic acids Mono octyl ester dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl dimethyl Tin, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester Antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as phosphorous acid Three aromatic ester, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as season penta Tetrol, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer is such as co-precipitated metallic soap, liquid metals Soap compound stabilizer, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate two Normal-butyl tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.

Toughener in the auxiliary agent for adding/using can reduce polymer material brittleness, increase toughness, carry High material bearing strength comprising but be not limited only to following any or appoint several toughener：Methyl methacrylate-fourth two Alkene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, propylene Nitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, benzene Ethylene-butadiene-styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene (ABS) copolymerization Object (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), methyl methacrylate-butadiene-styrene copolymerization Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.

Lubricant in the auxiliary agent for adding/using can improve material lubricity, reduce friction, reduce boundary Face adhesion property comprising but be not limited only to following any or appoint several lubricants：Saturated hydrocarbons and halogenated hydrocarbon, such as solid stone Wax, microcrystalline wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid, hydroxy stearate Acid；Fatty acid ester, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide Class, such as stearmide or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamides；Fat Alcohol and polyalcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, Magnesium stearate, zinc stearate etc..Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, institute Lubricant quantity is not particularly limited, generally 0.5-1wt%.

Releasing agent in the auxiliary agent for adding/using, it can make polymer samples be easy to demould, surface is smooth, It is clean comprising but be not limited only to following any or appoint several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon Oil, methyl phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon Rubber, polyvinyl alcohol etc..Wherein, the preferred dimethicone of releasing agent, polyethylene glycol, remover dosage used do not limit especially It is fixed, generally 0.5-2wt%.

Plasticizer in the auxiliary agent for adding/using, can increase the plasticity of polymer material so that polymerization Hardness, modulus, softening temperature and the brittle temperature of object decline, and elongation, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fat Fat esters of gallic acid, such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite Esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyls) oneself Ester, epoxy soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box acetylated castor oil Sour methyl esters, dihydric alcohol lipid, such as C_5~9Sour glycol ester, C_5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, Trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP), plasticizer consumption used do not limit especially It is fixed, generally 5-20wt%.

Foaming agent in the auxiliary agent for adding/using can make polymer samples foaming pore-forming, to obtain matter Gently, heat-insulated, sound insulation, flexible polymer material comprising but be not limited only to following any or appoint several foaming agents：Object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, dichloromethane, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitros, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, disalt Base lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, tristearin Acyl chlorides, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitros (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.

Dynamic regulation agent in the auxiliary agent for adding/using, can promote the dynamic of dynamic aggregation object, one As be the compound with free hydroxyl or free carboxyl group, include but are not limited to water, sodium hydroxide, alcohol, carboxylic acid, Louis Acid etc..The dynamic of polymer can be adjusted by adding this analog assistant, to obtain the expected performance of optimization.

Antistatic agent in the auxiliary agent for adding/using can draw the deleterious charge assembled in polymer samples It leads or eliminates, make it not to producing and life brings inconvenience or endangers comprising but be not limited only to following any or appoint several Antistatic agent：Anionic antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethyl Alcohol amine salt, to nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethylammonium perchlorate；Amphoteric ion type antistatic agent, such as alkane Base dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammoniums acetyl (N '-alkyl) amine second inner salt, N- lauryls- Bis- polyethylene oxide base-N- ethylphosphonic acids sodium of N, N-, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol epoxy It is ethane additive product, fatty acid ethylene oxide addition product, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, sweet Oil and fat acid esters；Polymer Antistatic Agent, such as polyene propionamide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- acetonyl pyrroles Pyridine phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, alkyl phosphate diethanol amine Salt (antistatic agent P).Antistatic agent dosage used is not particularly limited, generally 0.3-3wt%.

Emulsifier in the auxiliary agent for adding/using can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitute phase between surface tension, be allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to Under it is any or appoint several emulsifiers：Anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkylnaphthalene Sodium sulfonate, 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；Both sexes from Subtype, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol Polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol resin Fat acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecane Base benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used do not have It is particularly limited to, generally 1-5wt%.

Dispersant in the auxiliary agent for adding/using enables to solid flocculation group point in mixed with polymers liquid It dissipates and is suspended in liquid for tiny particle, those are poorly soluble solid and liquid particles in liquid for uniform dispersion, simultaneously Also it can prevent the sedimentation and cohesion of particle, be formed and stabilize suspension comprising but be not limited only to following any or appoint several points Powder：Anionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as fat Fat alcohol polyoxyethylene ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Macromolecule Type, such as starch, gelatin, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignin sulfonic acid Salt, polyvinyl alcohol etc..Wherein, the preferred neopelex of dispersant, naphthalene system methylene sulfonate (dispersant N), fat Alcohol polyoxyethylene ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.

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

Fluorescent whitening agent in the auxiliary agent for adding/using can make contaminated substance obtain the glittering of similar fluorite Luminous effect comprising but be not limited only to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, Pyrazoline type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent Bis- (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN) of (fluorescent brightener CBS), 4,4-, 2,2- (4,4 ' - Diphenylethyllene) dibenzoxazine (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002-0.03wt%.Delustering agent in the auxiliary agent for adding/using enables to incident light to reach polymer surfaces When, diffusing reflection occurs, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several disappear Photo etching：Settle barium sulfate, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, delustering agent It is preferred that silica, delustering agent dosage used is not particularly limited, generally 2-5wt%.

Fire retardant in the auxiliary agent for adding/using, can increase the flame resistance of material comprising but not only limit In following any or several fire retardants：Phosphorus system, as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, Phosphate toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Have Machine halide, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；It is inorganic fire-retarded Agent, such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos Propyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, and one As be 1-20wt%.

Nucleating agent in the auxiliary agent for adding/using can accelerate knot by the crystallization behavior of change polymer Brilliant rate increases crystal density and promotes fine grain size, reach shorten material molding cycle, improve the product transparency, The purpose of the physical mechanical properties such as lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, packet It includes but is not limited only to following any or appoints several nucleating agents：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid Sodium, silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, nucleating agent is preferred Silica, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.

It is good can to ensure that polymer has during film for rheological agent in the auxiliary agent for adding/using Brushability and coating thickness appropriate, prevent storage when solid particle sedimentation, its redispersibility can be improved comprising but It is not limited only to following any or appoints several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, carbonic acid Calcium, lithium chloride, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silicon dioxide；Organo-metallic compound is such as hard Resin acid aluminium, aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, as organobentonite, castor oil derivative, cellulose derive Object, isocyanate derivates, acrylic emulsion, acrylic copolymer, polyvinyl alcohol, polyethylene wax, cellulose esters etc..Wherein, It is preferred that organobentonite, polyethylene wax, hydrophobically modified alkalinity swellable emulsions (HASE), alkali-swellable emulsions (ASE), used Rheological agent dosage be not particularly limited, generally 0.1-1wt%.

Thickener in the auxiliary agent for adding/using, can assign the good thixotropy of mixed with polymers liquid and Consistency appropriate, to meet various need such as its stability and application performance during production, storage and use It asks comprising but be not limited only to following any or appoint several thickeners：Lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxy Ethylene ether sulfate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid isopropyl acyl Amine, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, manually Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch, Seaweed acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, Polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc..Wherein, the preferred hydroxyethyl cellulose of thickener, coconut oil diethanol Amide, acrylic acid-methacrylic acid copolymer, thickener dosage used are not particularly limited, generally 0.1-1.5wt%.

Levelling agent in the auxiliary agent for adding/using can ensure that the flat smooth of polymer coating film is uniform, change Kind film coated surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents：Acetic acid-butyric acid Cellulose, polyacrylate, organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used do not have It is particularly limited to, generally 0.5-1.5wt%.

The filler for adding/using, primarily serves following effect in the polymeric material：1. reducing molding system The shrinking percentage of part improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting The viscosity of material；3. meeting different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, carries High-wearing feature improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. it is steady to assign light Qualitative and chemical resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.

The filler for adding/using, selected from following any or several fillers：Inorganic non-metallic filler, gold Belong to filler, organic filler.

The inorganic non-metallic filler for adding/using includes but are not limited to following any or appoints several：Carbon Sour calcium, clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos are fine Dimension, orthoclase, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, two sulphur Change molybdenum, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, powder Coal ash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass microballoon, Foam microspheres, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanate Fiber, carbon silica fibre, ceramic fibre, whisker etc..

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

The organic filler added/used includes but are not limited to following any or appoints several：Fur, day T PNR, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, Cellulose nanocrystal body, cellulose acetate, shellac, crust Element, chitosan, lignin, starch, protein, enzyme, hormone, raw lacquer, wood powder, shell powder, glycogen, xylose, silk, artificial silk, dimension Nylon, phenolic aldehyde microballon, resin microbeads etc..

Wherein, the wire feeding that can be added/use does not limit, mainly depending on required material property, preferred carbon Sour calcium, clay, barium sulfate, talcum powder, carbon black, graphene, graphene oxide, carbon nanotube, Cellulose nanocrystal body, (hollow) Glass microballoon, foam microspheres, glass fibre, carbon fiber, metal powder, natural rubber, velveteen, resin microbeads, filler used are used Amount is not particularly limited, generally 1-30wt%.

In the preparation process of dynamic aggregation object material, the preferred antioxidant of auxiliary agent that can add/use, light stabilizer, heat Stabilizer, toughener, plasticizer, foaming agent, fire retardant, dynamic regulation agent.It is the preferred calcium carbonate of filler that can add/use, viscous Soil, barium sulfate, talcum powder, carbon black, glass microballoon, graphene, graphene oxide, carbon nanotube, Cellulose nanocrystal body, glass Fiber, 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 (IV), compound (V), usually also need Initiator to be optionally added in a solvent cause polymerization in a manner of polymerisation in solution and obtain dynamic aggregation object, or be added point Powder and oil-soluble initiator are configured to suspension and obtain dynamically gathering to cause polymerization in a manner of suspension polymerisation or slurry polymerization Object is closed, or addition initiator and emulsifier are configured to emulsion and obtain dynamic aggregation in a manner of emulsion polymerization to cause polymerization Object.Used polymerisation in solution, suspension polymerisation, slurry polymerization and emulsion polymerization method, be those skilled in the art 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-vinegar Vinyl acetate oligomer, polyacrylic acid N-butyl oligomer, atoleine etc.；The plasticizer can be selected to add/using Auxiliary agent in plasticizer described in classification, which is not described herein again；The ionic liquid is generally by organic cation and inorganic Anion forms, cation be usually alkyl quaternary ammonium ion, alkyl quaternary see ion, the substitution of 1,3- dialkyl group imidazol ion, N- Alkyl-substituted pyridinium ion etc.；Anion 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, when preparing dynamic aggregation object using deionized water and selecting to be retained, water-setting can be obtained Glue；When preparing dynamic aggregation object using organic solvent and selecting to be retained, organogel can be obtained；Using oligomer come When preparing dynamic aggregation object and selecting to be retained, oligomer swell gel can be obtained；It is poly- that dynamic is prepared using plasticizer When closing object and selecting to be retained, plasticizer swell gel can be obtained；Dynamic aggregation object is prepared using ionic liquid and is selected It selects when being retained, ionic liquid swell gel can be obtained.

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

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 (IV), compound (V), usually also need It is 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 institute The melt polymerization of use, the method for gas-phase polymerization, are well known to those skilled in the art and widely used polymerization, It 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, the change of selected organoboron compound (I), the primitive containing monohydroxy Object (II), compound (III), compound (IV), compound (V) is closed can flexibly to hold at component selections and formula rate, but It should reasonably be set according to target material performance and the structure of selected compounds, the reactive group number contained and molecular weight Meter and combination.Wherein, the compound (II) of the organoboron compound (I), the primitive containing monohydroxy that are added, is changed compound (III) Close object (IV), compound (V) should ensure that the molar equivalent of functional group and/or other reactive groups in reactant system than at In range appropriate.The single hydroxyl contained in organoboron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III) Range of the molar equivalent than preferably 0.1~10 of base primitive and organic boronic primitive functional group, more preferable 0.3~3 range, more It is preferred that 0.8~1.2 range.Contain when in organoboron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III) The molar equivalent ratio of some functional groups is close to 1:When 1, the dynamic aggregation object that the extent of reaction is high, stability is good can be obtained；When having The molar equivalent ratio for the functional group contained in machine boron compound (I), the compound (II) of the primitive containing monohydroxy, compound (III) Deviate 1:When 1, then the preferable dynamic aggregation object material of dynamic can be obtained.Similarly, when selection compound (IV), compound (V) when preparing dynamic aggregation object as reactive component, the molar equivalent ratio of other reactive groups should also be located in reactant system In range appropriate, range of the molar equivalent than preferably 0.1~10 of other reactive groups of polymerisation is carried out, more preferably 0.3~3 range, more preferable 0.8~1.2 range.In actual fabrication process, those skilled in the art can be according to reality It needs to be adjusted.

Dynamic aggregation object in the present invention is due to having dynamic organic boronic ester bond and optional supermolecule hydrogen bond so that The dynamic aggregation object obtained has certain dynamic reversibility and good toughness, is set by suitable component selection and formula Meter, material can be applied to military aerospace equipment, functional coating, biological medicine, bio-medical material, the energy, building, bionical, intelligence The fields such as energy material, have broad application prospects.

For example, making full use of self-repairability possessed by dynamic aggregation object, can prepare viscous with self-repair function Agent is tied, is applied to the gluing of various types of materials, also can be used as bulletproof glass squeegee；It can also be used for preparing and there is good plasticity simultaneously And the polymer that can recycle reuse blocks sealing elements such as glue and sealing-plug, sealing ring etc., or it is wear-resisting and anti-using preparing Tear taper knob etc.；Dynamic reversibility based on organic boronic ester bond and side hydrogen bond can be designed and be prepared with selfreparing work( The scratch resistant coatings of energy are realized and are protected to the long-effective corrosion of basis material to extend the service life of coating；By suitable Component selection and formula design, and polymer gasket or polymer plate with self-repair function can be prepared, so as to mould The principle of bionical object wound healing so that material can carry out self-healing to internal or outer damage, eliminate hidden danger, prolong The service life for having grown material shows huge application potential in the fields such as military project, space flight, electronics, bionical.

For another example the introducing of organic boronic ester bond and supermolecule hydrogen bond so that polymer material under external force can body Reveal excellent toughness, it is hereby achieved that thin polymer film, fiber or plank that toughness is splendid, be widely used in it is military, The fields such as space flight, movement, the energy, building；Also it can be used as shape-memory material, when the external force is removed, material The deformation generated in loading procedure can be restored；Also polymer material can be applied to make with creep properties and high-elastic Property conversion magic effect toy and body-building material.

Dynamic based on dynamic covalent bond and optional hydrogen bond, can obtain dilatancy, Neng Gouqi under external force To good energy-absorbing effect.Using the dynamic aggregation object as energy-absorbing material, a kind of good energy-absorbing method can be provided.It can It is applied to making damping shock absorber, for the vibration isolation of various motor vehicles, mechanical equipment, bridge, building, polymer For material when vibrated, the big energy that can dissipate plays damping, to effectively mitigate the vibrations of vibration body；By its As energy-absorbing buffering material, it is applied to amortizing packaging material, athletic protective article, the police protection material of surge guard product and army Material etc., to reduce article or human body suffered under external force vibrations and impact, including the impact that explosion generates Wave etc..Therefore, using the dynamic aggregation object as energy-absorbing material, a kind of excellent energy-absorbing method can be provided.

In addition, it may also be used for the speed lockup's device for preparing road and bridge can be also used for making antidetonation shear plate or follow Zernike annular polynomial carrying tool, or for making stress monitoring sensor.

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

Weigh a certain amount of binary organic boric acid compounds 1 (using ethyl-lithium, vinyl lithium with trimethylborate the system of reacting Obtain ethylethylene ylboronic acid；It is catalyst by initiator, triethylamine of AIBN, using ethylethylene ylboronic acid and 1, oneself two sulphur of 6- Alcohol is made by thiol-ene click-reactions) it is dissolved in the solution that 0.5mol/L is configured in tetrahydrofuran solvent；It weighs certain The end hydroxypropyl polydimethylsiloxanediols diols of amount are dissolved in the solution that 0.1mol/L is configured in tetrahydrofuran solvent.Take 10mL Tetrahydrofuran solution dissolved with binary organic boric acid compounds 1 is added in the reaction bulb of dried and clean, and a small amount of second is added dropwise Acid is stirred 15min, after be slowly added into wherein again 50mL dissolved with end hydroxypropyl polydimethylsiloxanediols diols tetrahydrochysene Tetrahydrofuran solution, the triethylamine of 2mL, is stirred 10min.Above-mentioned mixed solution is constantly stirred under the conditions of 80 DEG C, The water that reaction generates constantly is excluded in reaction process, with the progress of stirring, the viscosity of solution constantly rises, and after stirring 4h, obtains To homogeneous dynamic aggregation logistics body.The apparent viscosity of polymer fluid is tested using rotational viscometer, wherein test Temperature is 25 DEG C, and constant shear rate is 0.1s^-1, the apparent viscosity for measuring polymer fluid is 1038mPas.Dynamic aggregation Object imparts polymer fluid with the effect of " shear thickening ".This polymer can be applied to the explosion-proof of flammable liquid, in liquid After middle addition polymer, flammable liquid, since viscosity increases, is not likely to produce splashing, to increase during stirring use Safety.

Embodiment 2

Ethyl dichloride boron is hydrolyzed into ethyl-boron dihydroxide in acid condition first, then under triethylamine catalysis, passes through second Ylboronic acid synthesizes the dihydric alcohol 1 containing organic boronic ester bond with the esterification of alcohol with 1,4-butanediol by organic boronic, control The amount ratio of ethyl dichloride boron processed and 1,4- butanediol substances is 1:2；By the dihydric alcohol 1 obtained containing organic boronic ester group with Excessive hexamethylene diisocyanate obtains containing organic boric acid ester under the catalysis of dibutyl tin laurate in 85 DEG C of copolymerization The polyurethane diisocyanate 2 of key；Again by the polyurethane diisocyanate 2 of propilolic alcohol and the key containing organic boric acid ester with substance Amount ratio be 2:1 reaction obtains the polyurethane containing the organic boronic ester bond pair alkine compounds 3 of double propinyl sealing ends.It will contain There are the double alkine compounds 3 of the polyurethane of organic boronic ester bond, 1,11- diazido -3,6,9- trioxaundecanes to dissolve respectively The solution of 0.1mol/L is configured in tetrahydrofuran solvent.The round-bottomed flask of a dried and clean is taken, addition 20mL, which contains, to be had Three oxygen of tetrahydrofuran solution and 20mL 1,11- diazidos -3,6,9- of the polyurethane pair alkine compounds 3 of machine boric acid ester bond Miscellaneous undecanoic tetrahydrofuran solution, the n,N-diisopropylethylamine of 0.45mL, after sealing, using bubbling argon deoxygenation 1h, so Utilizing syringe afterwards, (cuprous iodide of 2.02mg is dissolved in 20mL tetrahydrofurans by the monovalence configured copper-tetrahydrofuran solution In solvent) it is added in reaction bulb.Reaction bulb is heated to 55 DEG C, reacts 5d in the state of stirring, obtains that there is cyclic annular knot Structure dynamic aggregation object.The dynamic aggregation object material can be used for having the polyurethane coating material of self-repair function to use.

Embodiment 3

It weighs and a certain amount of (utilizes n-BuLi, vinyl lithium and boric acid three containing organic boron acidic group and hydroxy compounds 1 Butylethylene ylboronic acid is made in methyl esters reaction；Be catalyst by initiator, triethylamine of AIBN, using butylethylene ylboronic acid with 2 mercapto ethanol is made by thiol-ene click-reactions) it is dissolved in the solution that 0.5mol/L is configured in tetrahydrofuran solvent； A certain amount of binary organic boric acid compounds 2 are weighed again (to react with trimethylborate using n-BuLi, vinyl lithium and fourth is made Base vinyl boronic acids；It is catalyst by initiator, triethylamine of AIBN, it is logical using butylethylene ylboronic acid and Isosorbide-5-Nitrae-succinimide mercaptans Thiol-ene click-reactions are crossed to be made) it is dissolved in the solution that 0.5mol/L is configured in tetrahydrofuran solvent.Take a drying clean Net round-bottomed flask, be added 16g polypropylene oxide glycols (molecular weight is about 1600), after under nitrogen protection, in stirring The lower tetrahydrofuran solution that 20mL binary organic boric acid compounds 2 are added and 10mL contain organic boron acidic group and hydroxy compounds 1 Tetrahydrofuran solution, then a small amount of acetic acid is added dropwise and is stirred 30min, after instill a small amount of catalyst of triethylamine again, stirring is equal Flow back after even in 80 DEG C 2-3h, and constantly excluding the water that reaction generates in reaction process reacts with the progress of reaction on fluid viscosity It rises, finally obtains thick liquid.Place it in 50 DEG C of baking ovens and be dried for 24 hours except solvent, can finally obtain have compared with The polymer samples of big viscosity, can be as a kind of thermoplastic adhesive for rubber, the bonding of plastic or other material.

Embodiment 4

The macromolecular bifunctional vinyl compound of the key containing organic boric acid ester of 5mmol is added in the round-bottomed flask of dried and clean (first Acrylate polyethylene glycol monoester is obtained by the reaction by the acrylic acid of 1 molar equivalent and the polyethylene glycol of 1 molar equivalent；Utilize phenyl For dichloride boron with Acrylate polyethylene glycol monoester using benzene as solvent, triethylamine is catalyst, and reacting 2h in 80 DEG C is made), lead to nitrogen Gas shielded, the dichloromethane solvent that 60mL is added are stirred dissolving, add a small amount of photoinitiator DMPA and a small amount of and resist Oxygen agent BHT, stirs evenly；In addition after taking the ethanthiol of 5mmol, 20mL dichloromethane solvents to be configured to solution, in stirring shape Injected in round-bottomed flask by injection under state, with ultraviolet light 1h, after reaction solution filter except solvent obtains head product. Utilize petroleum ether/dichloromethane (4:1) decontamination is eluted, then obtains the poly- of solid sheet after dry 12h under the conditions of 60 DEG C Close object sample.It in the present embodiment, can be using polymeric articles as the thickener with dilatancy.

Embodiment 5

The polyethylene glycol of 6g phenyl boric acids sealing end is weighed (using 3- amino phenyl boric acid as raw material, by the poly- second of itself and dibromo sealing end Glycol is made using potassium carbonate as catalyst by hydrocarbyl reaction) it is added in the three-necked flask of dried and clean, add 60mL Methanol solvate, 15g polybutadiene diols (molecular weight is about 3000), is added dropwise a small amount of acetic acid, is raised to temperature after stirring evenly 80 DEG C, then 2mL triethylamines are added dropwise to, it is stirred at reflux 4h, the water that reaction generates constantly is excluded in reaction process, finally obtaining has The polymer fluid of certain viscosity.Then the polymer fluid of 100 mass parts is taken, the expandable polymer of 1.5 mass parts is added Microballoon quickly stirs to bubble is generated through professional equipment, is then injected into mold rapidly, places 30min at room temperature, then 4h is placed at 80 DEG C, and polybutadiene-base foamed polymer is obtained after demoulding.The foamed polymer tensile strength is 2.65MPa, Elongation at break 577%, density：98kg/m³.The foamed product can be used as automobile shock component, reduce in driving process Vibrations, while also there is selfreparing and recuperability.

Embodiment 6

It takes 2.5g cyclohexyl dichloride boron to be added in the reaction bulb of dried and clean, 120mL dichloromethane solvents is added, add Heat is stirred dissolving to 60 DEG C, be slowly added under stirring 35g polyurethane dihydric alcohol (using triethylamine as catalyst, Hexamethylene diisocyanate is reacted with excessive 1,4-butanediol to be made), after being stirred 10min, 2mL triethylamines are added, Continue to be stirred to react 3-5h in 80 DEG C under nitrogen protection, the hydrogen chloride that reaction generates constantly is excluded in reaction process, finally To the reaction solution with certain viscosity.Reactant is poured into suitable mold afterwards, is placed in 60 DEG C of vacuum drying ovens dry For 24 hours, it is cooled to later and is placed at room temperature for 30min, obtain gelatinous polymer samples.Polymer samples case hardness is relatively low, can be with It outer force effect to extend, also there are good self-healing properties.It in the present embodiment, can be using polymeric articles as sealing Glue is applied to the sealing of building filleting, the encapsulation process of electronic component.

Embodiment 7

22g polycarbonate glycol is added in three-necked flask, 6.5g acid-based compounds containing borphenyl be (3 molar equivalents 1,3,5-triazines -2,4 of 3- vinylphenylboronic acids and 1 molar equivalent, for tri- mercaptan of 6- using AIBN as initiator, triethylamine is catalysis Agent is made by thiol-ene click-reactions), 150mL DMF solvents are heated to 80 DEG C and are stirred dissolving, 2mL tri- is added Ethamine continues to be stirred to react 6h under the conditions of 80 DEG C, the water that reaction generates constantly is excluded in reaction process, after the reaction was complete, is obtained To the polymer fluid for having certain viscosity.Then 2.9g Graphene powders are sequentially added, 0.1g neopelexes continue After being dispersed with stirring 30min, the bentonite of 0.06g is added, ultrasound 5min is carried out, is stirred for 30min, it is suitable to be then poured into Mold in, be placed in 80 DEG C of vacuum drying ovens that the reaction was continued for 24 hours, be cooled to and be placed at room temperature for 30min, finally obtain and be dispersed with graphite The solid-state dynamic aggregation object sample of alkene.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, is utilized Cupping machine carries out extension test, and rate of extension 50mm/min, it is 16.63 ± 0.31MPa to measure sample tensile strength, is broken It is 128 ± 55% to split elongation.In the present embodiment, polymer samples can be made to one kind with self-repair function and with weight The graphene thermally conductive sheet of multiple power of regeneration is used.

Embodiment 8

15g acrylate random copolymers are added in three-necked flask (using AIBN as initiator, by (4- ethenylphenyls) Methanol, N-isopropylacrylamide, butyl methacrylate are obtained at 70 DEG C by free radical polymerization), 150mL tetrahydrofurans are molten Agent, be heated to 50 DEG C be stirred dissolving after, 4.8g ethylene glycol-hexamethylene ylboronic acid copolymer is added and (passes through ethylene glycol and hexamethylene The amount of the substances such as ylboronic acid polymerize to obtain), after being stirred 30min, 2mL triethylamines are added, continue to stir under the conditions of 80 DEG C 1.5-2h is reacted, the water that reaction generates constantly is excluded in reaction process.After reaction, solvent is sloughed by decompression suction filtration to obtain Dynamic aggregation object.In the present embodiment, can by polymer material with water carry out swelling for make can selfreparing and with buffering The hydrogel of effect.

Embodiment 9

Take a certain amount of dendritic polynary organic boric acid compounds 1 (using DMPA as photoinitiator, ultraviolet light is light source, By triallyl phosphine and 1, after level-one intermediate product is made by thiol-ene click-reactions in 2- dithioglycols, then with three allyls Base phosphine continues through after two level intermediate product is made in thiol-ene click-reactions, then passes through thiol-ene with 1,2- dithioglycols Click-reaction is made three-level intermediate product, then is made level Four intermediate product with triallyl phosphine reaction, then with 1,2- dithioglycols Pyatyi intermediate product is made by thiol-ene click-reactions, finally passes through thiol-ene click-reaction systems with vinyl boronic acids Obtain final product) it is dissolved in the solution that 0.01mol/L is configured in toluene solvant；Meanwhile taking a certain amount of adipate glycol Polyester diol-n-propyl boric acid copolymer (using adipic acid and ethylene glycol as raw material, passes through esterification synthesizing adipic acid second two Then the n-propyl boric acid of the amount of equal substances is copolymerized with adipate glycol polyester diol and is made by alcohol polyester diol) plus Heat of solution is configured to the solution of 0.24mol/L in toluene solvant.Take the molten of the dendritic polynary organic boric acid compounds of 20mL 1 The solution of liquid and 20mL adipate glycols polyester diol-n-propyl boric acid copolymer is added to the reaction bulb of dried and clean In, it is stirred evenly under the conditions of 80 DEG C, adds 2.5mL triethylamines, be stirred to react 4h under the conditions of 80 DEG C, in reaction process not The disconnected water for excluding reaction and generating.After reaction, the apparent viscosity of polymer fluid is tested using rotational viscometer, In, test temperature is 25 DEG C, and constant shear rate is 0.1s^-1, the apparent viscosity for measuring polymer fluid is 15300mPas, It can show sensitive dilatancy under stress/strain effect.A beaker separately is taken, the deionization of 60mL is added wherein Water, 0.4g neopelexes, 0.3g bentonite, 0.1g stearic acid and 0.1g oleic acid, after stirring by mixing, take 30mL polymer fluids are quickly fully stirred with solution progress, and dynamic aggregation object lotion finally can be obtained, can be applied It is distributed on fabric, is fabricated to shock resistance energy-absorbing protective articles.

Embodiment 10

A certain amount of 4,4'- dimercaptos diphenyl ether is weighed, the solution for being configured to 0.3mol/L in dichloromethane is dissolved in；Again The triene compound 1 of a certain amount of key containing organic boric acid ester is weighed (by the 4- vinylphenylboronic acids of 1 molar equivalent and 2 moles The propenyl of equivalent occurs esterification and is made under alkaline condition) it is dissolved in and is configured to the molten of 0.2mol/L in dichloromethane Liquid.The round-bottomed flask for taking a dried and clean is separately added into 4, the 4'- dimercapto hexichol ethereal solutions of 20mL and contains organic boric acid ester The solution of the triene compound 1 of key leads to nitrogen protection, is added a small amount of BHT antioxidant afterwards, suitable DMPA photoinitiators, Ultraviolet light under stirring, the time for controlling reaction make the extent of reaction in gel point hereinafter, being made with hyperbranched Final product, with the progress of reaction, reaction fluid viscosity rises, and final product shows more viscous pasty state, product is imported In mold, bulk polymer sample is finally obtained for 24 hours in 50 DEG C of dryings under vacuum condition, the vitrifying for the general plastics having Transition temperature and melting temperature, are broken and are had no progeny, be placed in 80 DEG C of baking ovens heating place 6-8h can again adhesion-molded (this process In may be selected that section slightly soak), can be also again molded, can be made into recyclable and review one's lessons by oneself by heating Multiple packing box uses.

Embodiment 11

The four arm polyethylene glycol of 25.86g are added (with pentaerythrite, ethylene oxide in the round-bottomed flask for taking a dried and clean For raw material, boron trifluoride ether is catalyst, the four arm polyethylene oxide blocked by cation ring-opening polymerization synthesis of hydroxy), 30g deionized water stirring and dissolvings are added, the alkyl-blocked polyethylene glycol oligomers of 100g, 6.52g binary organic borons is then added Acid compound (with ethylene methacrylic ylboronic acid and 1,6- ethanthiols are clicked by thiol-ene and are made), stirring is equal at normal temperatures It is even, it is warming up to 80 DEG C until completely dissolved, 2mL triethylamines are then added, continues to be stirred to react 2-4h, finally obtains polyethylene glycol Oligomer is swollen dynamic aggregation object gel.The gelatin polymer soft texture has self-repairability and good biocompatibility, It can be as Wound care film and applied to medical nursing field.

Embodiment 12

The diamine for weighing 5.42g keys containing organic boric acid ester (is original with ethylene methacrylic ylboronic acid, aminoothyl mercaptan Material is made aminoboronic acid compound by thiol-ene click-reactions under the conditions of 80 DEG C, then itself and 4- Aminophenethyl alcohols is led to Condensation reaction is crossed to be made), 150mL solvent acetic acid butyl esters are added, are heated to 50 DEG C of stirring and dissolvings；Then 18.64g polyurethane is added (hexamethylene diisocyanate, using dibutyl tin laurate as catalyst, controls six to group diisocyanate with 1,4-butanediol Methylene diisocyanate is excessive, is obtained in 85 DEG C of polymerizations), a small amount of catalyst dibutyltin dilaurylate is added, it is rear to control Temperature processed is 60 DEG C, continues to be stirred to react 4h, after reaction, reactant is poured into suitable mold, is placed in 60 DEG C very The reaction was continued in empty baking oven for 24 hours, is cooled to is placed at room temperature for 30min later, obtains block-like polymer samples.It is broken and breaks it Afterwards, section is glued and placed in 80 DEG C of placement 6h, polymer samples can be molded again (may be selected to omit section during this Micro- wetting), there are self-healing properties.Polymer samples have certain intensity and toughness, it is made into 80.0 × 10.0 × The dumbbell shape batten of (2.0~4.0) mm sizes carries out extension test using cupping machine, and rate of extension 50mm/min is surveyed Sample tensile strength is 9.28 ± 0.21MPa, stretch modulus is 12.35 ± 0.35MPa, elongation at break up to 266 ± 85%.In the present embodiment, the self-repairability embodied using polymer material and good mechanical performance, can will be made Polymer material as with self-repair function gear material.

Embodiment 13

Methyl acrylate-phenyl boric acid-N-isopropylacrylamide random copolymerization of 5.50g is weighed in the beaker of dried and clean Methyl acrylate, 3- vinylphenylboronic acids, N-isopropylacrylamide (using AIBN as initiator, are passed through RAFT radical polymerizations by object Conjunction obtains), the tetrahydrofuran of 120mL is added wherein, is placed under the conditions of 50 DEG C constantly stirring and dissolving, after dissolving completely, It is wherein added dropwise to the NaOH solution of a small amount of 1mol/L, is stirred 30min, forms the acrylic acid that side group contains phenyl boric acid trisodium base Methyl esters-phenyl boric acid sodium-N-isopropylacrylamide random copolymer solution.Weigh the polypropylene oxide monomethyl ether sealing end of 9.26g (it is hydroxyl by waiting amount ratio of substances that one end is obtained by the reaction to first pass through ethylene glycol with phenylboric acid to ethylene glycol-phenyl boric acid copolymer One end is the organic boronic ester compounds 1 of boronate, then is carried out to organic boronic ester compounds 1 by polypropylene oxide monomethyl ether Single sealing end is made) it is slowly added to methyl acrylate-phenyl boric acid sodium-isopropyl acrylamide that above-mentioned side group contains phenyl boric acid trisodium base In amine random copolymer solution, mixing is made it dissolve by being stirred continuously in the process, after dissolving completely, a small amount of second is added dropwise Acid is uniformly mixed, and is placed in 80 DEG C of oil bath pans and is carried out heating reaction, after reacting 4h, is obtained with certain viscosity Polymer fluid.Sequentially add 0.65g Graphene powders, 0.08g neopelexes, after being dispersed with stirring 30min, into Row ultrasound 15min is further continued for stirring 30min so that Graphene powder is uniformly dispersed in a polymer matrix, will have later certain The polymer samples of viscosity are poured into suitable mold, the 4-6h that is placed in 80 DEG C of baking ovens that the reaction was continued under vacuum, it Postcooling finally obtains the blocky dynamic aggregation object sample for being dispersed with Graphene powder to 30min is placed at room temperature for.It has general modeling The dynamic aggregation object of the glass transition temperature and mechanical strength of material, gained also there is excellent electric conductivity and self-repairability to have simultaneously The dynamic aggregation object can be used for conductive material by excellent heat dissipation performance.

Embodiment 14

A certain amount of tetra functional organic boronic ester compounds 1 are weighed (to first pass through 1- cyclopentenyls boric acid with isopropanol to exist Esterification occurs under alkaline condition and generates 1- cyclopentenyl boric acid diisopropyl alcohol esters；Then purple using DMPA as photoinitiator Outer light is light source, and product 1- cyclopentenyls boric acid diisopropyl alcohol ester and Isosorbide-5-Nitrae-succinimide mercaptans are passed through thiol-ene click-reactions It is made), it is dissolved in methylene chloride, is configured to the solution of 0.1mol/L.The round-bottomed flask of a dried and clean is taken, is added The organic boronic of 40mL-enol modified silicon oil 2 (is reacted with trimethylborate by ethyl-lithium, vinyl lithium ethyl is made first Vinyl boronic acids；As raw material, control rubs the end hydrogen-based silicone oil for being about again 2500mPas using 2-M3BOL, viscosity You are than being 1:1, Si―H addition reaction is carried out under Pt catalytic conditions, one end is made to be the silicone oil that hydroxyl one end is silicon hydrogen, then with obtained Ethylethylene ylboronic acid and one end are that the silicone oil that hydroxyl one end is silicon hydrogen is raw material, and control molar ratio is 1:1, in Pt catalytic conditions Lower progress Si―H addition reaction is made), 120mL methylene chlorides are added, then tetra- officials of 5mL are slowly added dropwise in stirring at normal temperature dissolving The dichloromethane solution of energy degree organic boronic ester compounds 1, then a small amount of acetic acid is added dropwise, 2mL tri- is added after being stirred 30min Ethamine, after be warming up to 90 DEG C, back flow reaction 4-6h under stiring, the 4- that is placed under vacuum condition in 80 DEG C of baking ovens that the reaction was continued 6h is cooled to is placed at room temperature for 30min later, finally obtains pasta polymer samples, has lower melt viscosity, Ke Yizuo It is used for a kind of additive with lubricant effect.

Embodiment 15

Weighing a certain amount of biphenylboronic acids compound 1, (using DMPA as photoinitiator, ultraviolet light is light source, 4- sulfydryl benzene Boric acid is made with 1,4-butanediol diacrylate by thiol-ene click-reactions), it is dissolved in solvents tetrahydrofurane, matches The solution of 0.5mol/L is made；Polypropylene oxide triol (the molecular weight of 12.0g is added in the round-bottomed flask for taking a dried and clean About 3000), add 120mL tetrahydrofuran solvent stirring at normal temperature dissolving, after 6mL hexichol is slowly added under stirring The tetrahydrofuran solution of boronic acid compounds 1 adds 1mL triethylamines, and 80 are to slowly warm up to after so that each component is sufficiently mixed uniformly DEG C, the reaction was continued 4h constantly excludes the water that reaction generates in reaction process, obtains the polymer fluid with certain viscosity.Afterwards Product is imported in mold, finally obtains polymer bulk sample for 24 hours in 50 DEG C of dryings under vacuum condition, the general modeling having The glass transition temperature and melting temperature of material have good impact resistance and self-repairability, can also be by heating, pressurizeing Again it is molded, the protective shell that can be made into the valuable electronic product such as mobile phone, computer uses.

Embodiment 16

Take a certain amount of borphenyl acid-based compound 1 (by 4- vinylphenylboronic acids and three [2- (3- mercaptopropyloxies) second Base] for isocyanuric acid ester using AIBN as initiator, triethylamine is catalyst, be made by thiol-ene click-reactions), it is dissolved in In toluene solvant, it is configured to the solution of 0.25mol/L；A certain amount of 4,4', 4 "-trihydroxy triphenyl methanes is taken to be dissolved in first again In benzene solvent, it is configured to the solution of 0.25mol/L.The round-bottomed flask of a dried and clean is taken, it is acid-group that 20mL borphenyls are added The toluene solution for closing object 1, is then slowly added to the toluene of 4,4', the 4 "-trihydroxy triphenyl methanes of 44mL under stirring Solution is stirring evenly and then adding into 1.5mL triethylamines, after be to slowly warm up to 120 DEG C, the reaction was continued under stirring, reacted The water that reaction generates constantly is excluded in journey, with the progress of stirring, the viscosity of solution constantly rises；By polymer after reaction 4-6h Sample is poured into suitable mold, and sample is placed in 80 DEG C of vacuum drying ovens and carries out removing solvent for 24 hours, room temperature is cooled to later and puts 30min is set, non-rigid solid polymer samples are finally obtained.After being cut off, section is glued and placed in 80 DEG C of baking ovens and is placed 4-6h (may be selected to section slightly soak during this), and polymer samples can be molded again, have self-healing properties. It can also be put into suitable mold, re-workability is obtained by heating, pressurizeing.In the present embodiment, polymer material is utilized The self-repairability embodied and recyclable characteristic, can be applied to make by polymer material obtained has selfreparing work( Energy and recyclable household electrical appliances insulated product, daily necessities etc. are used.

Embodiment 17

16.3g organic boronic modifications by copolymerization isoprene rubber is weighed (using AIBN as initiator, by isoprene and but-1-ene- 4- boric acid is obtained by free-radical polymerized), the enol modified silicon oil of 10.5g (be about with 2-M3BOL, viscosity The end hydrogen-based silicone oil of 3000mPas is raw material, and control molar ratio is 2:1, progress Si―H addition reaction is made under Pt catalytic conditions, Molecular weight is about 6000), to be added to after carrying out mixing 20min in small-sized internal mixer, and 5g white carbons, 5g titanium dioxides, 0.05g is added Barium stearate, 0.15g 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 placed in It is crosslinked in 120 DEG C of baking oven, is taken out after reacting 2h, be cooled to and be placed at room temperature for 30min, be removed from the molds sample, finally Obtain the dynamic aggregation object material of rubbery state.It can be prepared into of different shapes with good plasticity according to die size Product, and stretching extension can be carried out in wide range, embody very excellent tensile toughness.It is made into 80.0 × 10.0 The dumbbell shape batten of × (2.0~4.0) mm sizes, using cupping machine carry out extension test, rate of extension 50mm/min, Measure sample tensile strength be 1.22 ± 0.21MPa, stretch modulus be 1.42 ± 0.34MPa, elongation at break be 1234 ± 245%.After surface of polymer material is delineated with blade, place it in 80 DEG C of vacuum drying ovens after placing 4-6h, cut It disappears and (may be selected that surface slightly soak during this), sample can carry out selfreparing.This polymer material is in normality Under can keep soft, and interim rigidity is shown when being impacted, and after an impact, and become normal flexible shape again State can be made into body protection product such as knee-pad, elbow support and helmet anti-impact using stress response characteristic possessed by sample Hit the uses such as protective layer.

Embodiment 18

Take 5.2g allyls pinacol borate-butyl acrylate random copolymer 1 (using AIBN as initiator, by allyl Ylboronic acid pinacol ester, butyl acrylate obtain random copolymer by RAFT free radical polymerizations), it is dissolved in 15mL toluene solvants In；It (is to cause with AIBN to take hydroxy-ethyl acrylate-ethyl 5- hexene -1- aminocarbamic acid esters random copolymer 2 of 6.6g again Hydroxy-ethyl acrylate, ethyl 5- hexene -1- aminocarbamic acids esters are obtained random copolymer by agent by RAFT free radical polymerizations) It is dissolved in 15mL toluene solvants.The round-bottomed flask of a dried and clean is taken, 15mL allyls pinacol borate-propylene is added A small amount of acetic acid is added dropwise in the toluene solution of acid butyl ester random copolymer 1, is stirred 15min, then under stirring slowly The toluene solution and 30mL of hydroxy-ethyl acrylate-ethyl 5- hexene -1- aminocarbamic acid esters random copolymer 2 of 15mL is added 1- butyl -3- methylimidazole hexafluorophosphates ([C₄MIM]PF₆) ionic liquid, 1.5mL triethylamines are stirring evenly and then adding into, it is rear slow Slowly 120 DEG C are warming up to, flow back 2-4h under stirring, and with the progress of reaction, the viscosity of solution constantly rises, and reaction terminates Polymer samples are poured into suitable mold afterwards, sample is placed in 80 DEG C of vacuum drying ovens and carries out removing solvent, Zhi Houleng for 24 hours But it arrives and is placed at room temperature for 30min, finally obtain ionic liquid dynamic aggregation object gel.The ion liquid polymer gel has good Flexibility, and can largely be extended, it is 1.66 ± 0.36MPa to measure sample tensile strength, and elongation at break is 745 ± 162%.Breaked sample applies stress in section part, and being placed in 80 DEG C of vacuum drying ovens section after heating 6-8h can weigh New bonding (may be selected to section slightly soak during this), has self-healing properties, also can be according to mould of different shapes Tool is molded material again.The ionic liquid dynamic aggregation object gel can be used as energy-absorbing buffering bed course to be applied to fine mould Have damping, and selfreparing can be carried out to it.

Embodiment 19

The random copolymer 1 for weighing 4.8g side groups base containing organic boric acid ester and isocyanate group (using AIBN as initiator, is incited somebody to action Vinyl boronic acids pinacol ester, isocyanates ethyl acrylate, butyl methacrylate obtain nothing by RAFT free radical polymerizations Advise copolymer, the ratio of control vinyl boronic acids pinacol ester and isocyanates acrylic acid ethyl ester monomer makes described common be total to Valence is crosslinked below gel point), it is dissolved in 20mL THF solvents.The round-bottomed flask for taking a dried and clean, is added 14.6g's Polybutadiene dihydric alcohol, 60mL THF solvents, stirring at normal temperature dissolving, after prepared 20mL side groups be added under stirring contain The THF solution and 1.5g organo montmorillonites of organic boronic ester group and the random copolymer of isocyanate group 1 are scattered in 10mL tetrahydrochysenes The solution of furans, after being stirred 15min, be added 2mL triethylamines, after be to slowly warm up to 85 DEG C, flow back 1.5h at 85 DEG C, after 120 DEG C are warming up to, the reaction was continued 1.5h constantly increases with the carry out system viscosity of reaction, and product is that thick can flow Liquid.Polymer samples are poured into suitable mold after reaction, is placed in 80 DEG C of vacuum drying ovens and is carried out for 24 hours except molten Agent is cooled to is placed at room temperature for 30min later, and finally obtained polymer samples are in rubber-like, have certain elasticity, and can be one Determine to extend in range.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, is tried using stretching It tests machine and carries out extension test, rate of extension 50mm/min, it is 2.68 ± 0.22MPa, stretch modulus to measure sample tensile strength For 2.96 ± 0.66MPa, elongation at break is 694 ± 86%.In the present embodiment, the polymer samples broken can be recycled Afterwards, section part is bonded and (may be selected to section slightly soak during this), be placed in 50 DEG C of mold and apply one Constant-pressure places 6-8h, and the crackle of sample joint place disappears.Polymer can be made to a kind of rubber sealing material use, embodied The self-repairability of polymer material and the barrier property of montmorillonite layer.

Embodiment 20

Weigh 5.4g side groups base containing phenyl boric acid random copolymer (using AIBN as initiator, 3- allyl amino carbonyl benzene Boric acid, ethyl acrylate are made by RAFT free radical polymerizations), it is dissolved in 20mL toluene solvants, a small amount of hydroxide is added Sodium is stirred 30min, obtains the toluene solution of the side group base random copolymer of trisodium containing phenyl boric acid.Take dried and clean Round-bottomed flask, is added the polysulfones dihydric alcohol of 13.32g, 60mL toluene solvants, stirring at normal temperature dissolving, after be added under stirring The toluene solution of above-mentioned side group trisodium containing the phenyl boric acid base random copolymers of 20mL, is added dropwise a small amount of acetic acid, is stirred 15min Afterwards, be added 2mL triethylamines, after be to slowly warm up to 120 DEG C, flow back 4h at 120 DEG C, continuous with the carry out system viscosity of reaction Increase.Polymer solution is poured into suitable mold after reaction, is placed in 80 DEG C of vacuum drying ovens and carries out removing solvent for 24 hours, It is cooled to later and is placed at room temperature for 30min, finally obtain the polymer samples of hard block, polymer is with certain intensity and just Property, and there is preferable toughness and shock resistance energy absorption capacity.It is made into the mute of 80.0 × 10.0 × (2.0~4.0) mm sizes Bell pattern item carries out extension test using cupping machine, and rate of extension 10mm/min, measuring sample tensile strength is 13.35 ± 0.32MPa, stretch modulus are 14.78 ± 0.62MPa, and elongation at break is 234 ± 55%.Prepared by the embodiment Dynamic aggregation object sample can be used as the car insurance bar having higher requirements to intensity and impact resistance and army and police's protective article etc. It uses.

Embodiment 21

It (is about 3000mPas with allyl ylboronic acid, viscosity that 12mL organic boronics modified silicon oil is added in three-necked flask End hydrogen-based silicone oil be raw material, control molar ratio be 2:1, progress Si―H addition reaction is made under Pt catalytic conditions, and molecular weight is about 6000), 150mL dichloromethane solvents are heated to 50 DEG C after stirring and dissolving, after that the ends 9mL hydroxypropyl is added under stirring is poly- 2mL triethylamines are added in dimethyl siloxane glycol after being uniformly mixed, after be to slowly warm up to 80 DEG C and reacted, reacted The water that reaction generates constantly is excluded in journey, the viscosity of solution constantly rises with the progress of stirring, after hybrid reaction 4h, obtains Polymer fluid with certain viscosity.Sequentially add 1.2g multi-walled carbon nanotubes (MWCNTs), 0.1g detergent alkylate sulphurs Sour sodium after being dispersed with stirring 30min, carries out ultrasound 15min, is stirred for 30min so that multi-walled carbon nanotube is in a polymer matrix It is uniformly dispersed.After be poured into suitable mold, be placed in 50 DEG C of vacuum drying ovens it is dry for 24 hours, be cooled to room temperature later and put 30min is set, the evenly dispersed soft dynamic aggregation object sample for having multi-walled carbon nanotube is finally obtained.Gained dynamic aggregation object has Good electric conductivity, when dynamic aggregation object is acted on by extraneous stress, electric conductivity changes, and can be incited somebody to action using this characteristic It is used as the sensor with stress monitoring function.

Embodiment 22

The Methyl Hydrogen Polysiloxane Fluid of 5.3mL organic boronics modification is added in the three-necked flask of dried and clean (with but-1-ene- The Methyl Hydrogen Polysiloxane Fluid that 4- boric acid, viscosity are about 2000mPas is raw material, and Si―H addition reaction system is carried out under Pt catalytic conditions ), a small amount of acetic acid is added dropwise, is stirred 30min, after be heated to 60 DEG C, then be added 11.4mL enols be modified methyl contain (Methyl Hydrogen Polysiloxane Fluid for being about 2000mPas using cyclobutenyl alcohol, viscosity carries out silicon to hydrogen silicone oil as raw material under Pt catalytic conditions Hydrogen addition is made), 30min is stirred in the state of heating, after so that each component is sufficiently mixed uniformly, 1mL triethylamines, heating is added To 80 DEG C of reaction 3h, the water that reaction generates constantly is excluded in reaction process.After reaction, obtain that there is the sticky of certain viscosity Sample, polymer samples are poured into suitable mold, the 4-6h that is placed in 80 DEG C of baking ovens that the reaction was continued under vacuum, it Postcooling finally obtains soft dynamic aggregation object sample to 30min is placed at room temperature for.Polymer samples are under slower rate of extension It can be stretched on a large scale, generate creep；If but Rapid stretching, demonstrate flexibility feature, is pressed it with finger After being capable of Fast Restoration.This material can be fabricated to the toy of different, with magic elasticity the similar plasticine of color.

Embodiment 23

The polysulfones dihydric alcohol of 18.8g is added in the three-necked flask of dried and clean, the dissolving of 120mLDMF stirring solvents is added, Then it is (anti-by being esterified with but-1-ene -4- boric acid and isopropanol that the more first boric acid ester compounds of 6.2mL are added under stirring Double bond containing boric acid ester compound should be prepared, then with double bond containing boric acid ester compound obtained and trimethylolpropane tris (3- Mercaptopropionic acid ester) it is raw material, AIBN is initiator, and triethylamine is catalyst, is made by thiol-ene click-reactions), 60 30min is stirred at DEG C, and after so that each component is sufficiently mixed uniformly, 1mL triethylamines are added, are warming up to 120 DEG C after mixing, continue React 3h.It is poured into after reaction in suitable mold, and sample is placed in 120 DEG C of vacuum drying ovens for 24 hours into traveling one The reaction and drying of step, are cooled to are placed at room temperature for 30min later, finally obtain the polymer material of hard block.Polymer-like Product surface is smooth, and has glossiness, has certain surface strength and rigidity.It is crushed to be placed in 120 DEG C of molds and be put After setting 16h, sample can be molded again.It is made into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, is utilized Cupping machine carries out extension test, and rate of extension 10mm/min, it is 10.88 ± 1.23MPa to measure sample tensile strength, is drawn It is 13.68 ± 2.42MPa to stretch modulus.Using characteristics such as its self-repairability and recuperabilities, electricity can be applied to Device, electronics, instrument, instrument and space flight and aviation etc..

Embodiment 24

A certain amount of triphenyl borine acid compound 1 is taken (to utilize 1,3,5- triaminobenzenes, (4- allyl aminos carbonyl) benzene boron Acid is raw material, and toluene is solvent, is made by the Michael addition reactions of alkene and amine), it is dissolved in toluene solvant, prepares At the solution of 0.2mol/L.The three arm polypropylene oxide triols of 12.4g are added in the three-necked flask of dried and clean (with 2,4,6- Trihydroxyethyl benzene, propylene oxide are raw material, and boron trifluoride ether is catalyst, and three arm polyoxies are synthesized by cation ring-opening polymerization Change propylene triol), the toluene that 120mL is added is stirred dissolving, and the acidification of 8.4mL triphenyl borines is then added dropwise under stirring The toluene solution for closing object 1, is added dropwise a small amount of acetic acid, stirs 30min at normal temperatures, after so that each component is sufficiently mixed uniformly, is added 2mL triethylamines continue to be warming up to 80 DEG C of reaction 90min after stirring evenly, the water that reaction generates constantly are excluded in reaction process, Solution viscosity constantly rises during reaction, until after reaction, obtaining the polymer samples of certain viscosity.It will glue Thick polymer samples pour into suitable mold, are placed in 50 DEG C of vacuum drying ovens and are dried for 24 hours, are cooled to room temperature later and put 30min is set, block-like dynamic aggregation object sample is finally obtained.It is made into the mute of 80.0 × 10.0 × (2.0~4.0) mm sizes Bell pattern item carries out extension test using cupping machine, and rate of extension 50mm/min, measuring sample tensile strength is 14.21 ± 0.22MPa, stretch modulus are 16.43 ± 0.35MPa, and elongation at break is 108 ± 43%.The dynamic aggregation object material Material can be used as the uses such as plank and all kinds of anisotropic materials, have lightweight, high-strength and self-healing properties and recuperability.

Embodiment 25

Taking 35g vinyl chloride-organic boronic ester copolymer, (3- methacryl amido phenyl boric acids are anti-by being esterified with isopropanol The monoene compound of the base containing organic boric acid ester should be synthesized, then using AIBN as initiator, by vinyl chloride and the base containing organic boric acid ester Monoene compound is made by free radical polymerization), and 70g vinyl chloride -4-Vinyl phenol copolymer (using AIBN as initiator, it will 4-Vinyl phenol and vinyl chloride pass through free-radical polymerized be made), 12g polyvinyl chloride, 20g o-phthalic acid dibutyl esters, 2.2g Fire retardant TPP, 1g stearic acid, 0.1g irgasfos 168s, 0.2g antioxidant 1010s, 0.2g di-n-butyltin dilaurates, 0.5g bis- Methyl-silicone oil after mixing, is added in small-sized extruder and carries out extrusion blending, and extrusion temperature is 140-160 DEG C, is obtained After extrusion batten is granulated, sample preparation is carried out using small injecting machine, injection temperature is 140-160 DEG C, then will be obtained Thin slice batten is placed in 120 DEG C of baking ovens and is crosslinked, and then takes out, is placed in mold, is placed under the conditions of 120 DEG C of nitrogen protections 4-6h is dried and further reacts, and finally obtains the dynamic aggregation object sample with flame retardant property.It is made into The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes carries out extension test, rate of extension using cupping machine For 50mm/min, it is 13.26 ± 1.12MPa to measure sample tensile strength, and stretch modulus is 15.34 ± 2.22MPa, extension at break Rate is 286 ± 102%, and sample has certain mechanical property and good anti-flammability.In addition, product obtained is also with good Good plasticity, can be shaped to the polymeric articles of different appearances according to mold of different shapes.In the present embodiment, can will gather It closes object sample to be made with the use of the plank of impact resistance and anti-flammability, and it can be recycled and reused.

Embodiment 26

Take 15g organic boric acid esters-propylene copolymer (using AIBN as initiator, by isopropenyl boric acid under the conditions of 80 DEG C Pinacol ester and propylene carry out random copolymerization and are made), 30g pentenols-random copolymer of propylene is (using AIBN as initiator, 80 4- amylene-1-ols and propylene random copolymerization is carried out under the conditions of DEG C to be made), 5.5g polypropylene, 5g MBS toughener, tri- oxygen of 0.5g Change two antimony, 0.5g stearic acid, 0.05g irgasfos 168s, 0.1g antioxidant 1010s, 0.1g di-n-butyltin dilaurates, 0.25g Dimethicone after mixing, is added in small-sized extruder and carries out extrusion blending, and extrusion temperature is 140-160 DEG C, is obtained Extrusion batten be granulated after, using small injecting machine carry out sample preparation, injection temperature be 140-160 DEG C, will then be made Thin slice batten be placed in 120 DEG C of baking ovens and be crosslinked, then take out, be placed in mold, transferred in 120 DEG C of nitrogen protection conditions It sets 4-6h to be dried and further react, finally obtains the dynamic aggregation object sample of toughening.It is made into 80.0 × The dumbbell shape batten of 10.0 × (2.0~4.0) mm sizes carries out extension test, rate of extension 50mm/ using cupping machine Min, measure sample tensile strength be 6.25 ± 1.13MPa, stretch modulus be 8.63 ± 1.88MPa, elongation at break be 366 ± 33%, polymer samples have good flexibility, can carry out large range of stretching.In addition, sample obtained is also with good Good plasticity, can be shaped to the polymeric articles of different appearances according to mold of different shapes.In the present embodiment, can will gather Conjunction object sample is made plastic pipe and is used, and can be recycled and reused to waste material.

Embodiment 27

The round-bottomed flask for taking a dried and clean, the organic boronic modified silicon oil that 14.4g is added (with allyl ylboronic acid, glue The end hydrogen-based silicone oil that degree is about 3000mPas is raw material, and control molar ratio is 2:1, Si―H addition reaction is carried out under Pt catalytic conditions It is made, molecular weight is about 6000), suitable dichloromethane solvent to be added, and the side group that 16.8g is added after stirring and dissolving carries amino The HTPB of carbamate group is (by end hydroxy butadiene (HTPB) and 2- t-butoxycarbonyl aminos ethyl mercaptan with HTPB side group double bonds Molal quantity：The sulfydryl molal quantity of 2- t-butoxycarbonyl amino ethyl mercaptans is 1:1.2 mixing, are then added relative to 2- tertiary butyloxycarbonyls The photoinitiator benzoin dimethylether (DMPA) of base aminoothyl mercaptan 0.2wt% after stirring fully, is placed in UV crosslinking instrument purple External radiation 4 hours obtains the HTPB that side group carries carbamate groups), then a small amount of triethylamine is added dropwise, it is uniformly mixed It is placed in 80 DEG C of oil bath pans and carries out heating reaction, the water that reaction generates constantly is excluded in reaction process.After reacting 4h, had There is the polymer fluid with certain viscosity；Sequentially add 2.85g Graphene powders, 0.15g neopelexes, stirring After disperseing 30min, ultrasound 15min is carried out, is further continued for stirring 30min so that Graphene powder is uniformly dispersed in a polymer matrix. The polymer samples with certain viscosity are poured into suitable mold later, are placed in 80 DEG C of baking oven relayings under vacuum Continuous reaction 4-6h, is cooled to is placed at room temperature for 30min later, finally obtain the soft dynamic aggregation object sample for being dispersed with Graphene powder Product.There is the dynamic aggregation object of gained excellent electric conductivity, the minimal stress acted on dynamic aggregation object can be become with electric current The form of change shows, and has the function of sensitive stress sensing.It in the present embodiment, can be by dynamic aggregation object application obtained In medical instrument stress sensing device.

Embodiment 28

30mL organic boric acid esters-enol modified silicon oil (methyl mercapto for being about 6000 with molecular weight is added in three-necked flask Base silicone oil, vinyl boronic acids pinacol ester, vinyl alcohol are raw material, using DMPA as photoinitiator, under the conditions of ultraviolet light, It is made by thiol-ene click-reactions), 120mL dichloromethane solvents are warming up to 80 DEG C after mixing, and the three of 2mL are added Ethamine carries out polymerisation under stirring.During polymerization, the viscosity of silicone oil constantly rises, and after reacting 2h, can obtain To the polymer fluid with certain viscosity.Then 2.56g Cellulose nanocrystals body (NCC) is added, is stirred 30min, then Ultrasonic 15min, is stirred for 30min so that Cellulose nanocrystal body is uniformly dispersed in a polymer matrix.After be poured into conjunction In suitable mold, the 4h that is placed in 80 DEG C of vacuum drying ovens that the reaction was continued is cooled to is placed at room temperature for 30min later, finally obtains dispersion It is in the polymer samples of rubber-like to have Cellulose nanocrystal body.It is made into the mute of 80.0 × 10.0 × (2.0~4.0) mm sizes Bell pattern item carries out extension test using cupping machine, and rate of extension 50mm/min, it is 7.5 to measure sample tensile strength ± 2.3MPa, stretch modulus are 9.8 ± 3.85MPa, and elongation at break is 435 ± 122%, and resulting polymers sample has both high-strength Degree and high-flexibility.It when defect occurs in its surface, is placed in 80 DEG C of vacuum drying ovens and heats 2-4h, defect disappears.In this implementation In example, the high intensity that has using it, high flexible and self-repairability can use it for super hot melt adhesive or self-adhesive at room temperature material Material uses, it can also be used to be used for bridge and road construction as the medium of speed lockup's device.

Embodiment 29

The reactor of a dried and clean is taken, the 1 (phenyl boric acid of bifunctional vinyl compound of a certain amount of key containing organic boric acid ester is added With dihydroxypropyl acetamide with the ratio of the amount of substance for 1:2 mixing, are made by esterification under alkaline condition), it is certain The N-isopropylacrylamide of amount, a certain amount of butyl methacrylate and initiator A IBN control the diene of boronic acid containing ester bond Close object 1, N-isopropylacrylamide, butyl methacrylate, AIBN substance amount ratio be 15:100:150:1, it is added appropriate Solvent anhydrous tetrahydro furan, be put into 70 DEG C of oil bath and react, with the progress of reaction, reaction fluid viscosity gradually increases, and controls Reaction time processed makes the extent of reaction in gel point hereinafter, obtaining the polymeric liquid with larger viscosity after reaction 8h.Then The polymeric liquid for taking 100 mass parts is swollen in the phosphate trimethylbenzene of the epoxidized soybean oil and 50 mass parts of 70 mass parts In ester mixed liquor, it is to obtain the polymer gel of plasticizer swelling to remove residual solvent tetrahydrofuran.In surface of polymer material It after being delineated with blade, places it in 80 DEG C of vacuum drying ovens after placing 2-3h, cut, which disappears, (may be selected during this to table Face slightly soak), sample can carry out selfreparing.Polymer samples also show excellent toughness, and elongation at break reaches To 5 times, there is excellent shock resistance energy absorption capacity.The polymer material can be applied to shape-memory material, toughness material, movement Protective article etc..

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, which is characterized in that it contains organic boronic ester bond；Wherein, the organic boronic ester bond is made For dynamic aggregation object polymerization linking point or crosslinking linking point or simultaneously as polymerization linking point and crosslinking linking point and In the presence of being the necessary condition to form or maintain dynamic aggregation object structure；And the dynamic aggregation object is in any one chain direction On at least contain 3 organic boronic ester bonds as chain backbone group；

Wherein, an organic boronic ester bond, and at least one carbon atom in structure are at least formed between boron atom and carbon atom It is connected with boron atom by boron carbon key, and at least one organic group is keyed to by the boron carbon in boron atom.

2. a kind of dynamic aggregation object according to claim 1, which is characterized in that the organic boronic ester bond is by organic boronic Primitive is formed with monohydroxy elementary reaction.

3. a kind of dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object chain topological structure Selected from line style, ring-type, branched, cluster, crosslinking and combinations thereof form.

4. a kind of dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object also includes super Molecule hydrogen bond action.

5. a kind of dynamic aggregation object according to claim 4, which is characterized in that form the supermolecule hydrogen bond action Hydrogen bond group contains following constituent：

6. a kind of dynamic aggregation object according to claim 1, which is characterized in that constitute dynamic aggregation object or its composition match Fang Zufen further include it is following any or appoint it is several can additive or usable object：Auxiliary agent, filler；

Wherein, the auxiliary agent is selected from following any or appoints several：Catalyst, initiator, antioxidant, light stabilizer, heat are steady Determine agent, toughener, lubricant, releasing agent, plasticizer, foaming agent, dynamic regulation agent, antistatic agent, emulsifier, dispersant, Toner, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent；

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

7. a kind of dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object or its composition tool There is following any character：Solution, lotion, cream, glue, ordinary solid, elastomer, gel, foam.

8. the dynamic aggregation object according to any one of claim 1 to 7, which is characterized in that it is applied to damper, buffering Material, defense of resistance to impact material, athletic protective article, army and police's protective article, force snesor, self-repairability coating, self-repairability Plank, self-repairability binder, bulletproof glass squeegee, toughness material, shape-memory material, sealing element, toy product.

9. a kind of method of energy-absorbing, which is characterized in that provide a kind of dynamic aggregation object and the progress energy-absorbing using it as energy-absorbing material； Wherein, the dynamic aggregation object contains organic boronic ester bond and optional supermolecule hydrogen bond；Wherein, described organic Boric acid ester bond is as the polymerization linking point or crosslinking linking point of dynamic aggregation object or simultaneously as polymerization linking point and friendship Join linking point and exist, is the necessary condition to form or maintain dynamic aggregation object structure；And the dynamic aggregation object is arbitrary At least contain 3 organic boronic ester bonds as chain backbone group on one chain direction；